TW201422442A - Methods for processing OLED devices - Google Patents

Abstract

Methods for making electronic devices on thin sheets (20) bonded to carriers (10). A surface modification layer (30) and associated heat treatments, may be provided on a sheet (20), a carrier (10), or both, to control both room-temperature van der Waals (and/or hydrogen) bonding and high temperature covalent bonding between the thin sheet and carrier during the electronic device processing. The room-temperature bonding is controlled so as to be sufficient to hold the thin sheet and carrier together during vacuum processing, wet processing, and/or ultrasonic cleaning processing, during the electronic device processing. And at the same time, the high temperature covalent bonding is controlled so as to prevent a permanent bond between the thin sheet and carrier during high temperature processing, during the electronic device processing, as well as maintain a sufficient bond to prevent delamination during high temperature processing.

Description

Method of processing OLED components

The present application claims the priority of U.S. Application Serial No. 14/047,514, filed on Oct. 7, 2013, and the U.S. Provisional Application No. 61/ filed on Dec. 13, 2012. The priority of 736,871, the contents of which is hereby incorporated by reference in its entirety in its entirety in its entirety in the the the the the the the the

The present invention is directed to an article and method for processing electronic components on a flexible sheet on a carrier, and more particularly to an article for processing electronic components on a flexible glass sheet on a glass carrier and method.

Flexible substrates offer the promise of using less expensive components for roll processing and the potential to make thinner, lighter, more flexible and more durable displays. However, the techniques, equipment, and processes required for the roll processing of high quality displays have not been fully developed. Since panel makers invest heavily in tool sets that process larger glass sheets, laminating flexible substrates to carriers and manufacturing the display elements by a single piece of continuous processing can be provided to create thinner, more A short-term solution to the value proposition of a lighter and more flexible display. A display has been shown on a polymer sheet, such as polyethylene naphthalate (PEN), where the component is fabricated as A one piece continuous form in which the PEN is laminated to a glass carrier. The upper temperature limit of PEN limits the quality of the components and the processes that can be used. In addition, the high permeability of the polymer substrate results in environmental degradation of the OLED element, where near gas seals are required. Film encapsulation provides a solution to overcome this limitation, but it has not been demonstrated that film encapsulation at larger volumes provides acceptable yields.

In a similar manner, display elements can be fabricated using glass carriers laminated to one or more thin glass substrates. It is expected that the low permeability of thin glass and improved temperature and chemical resistance will enable flexible displays with higher performance and longer life.

However, for thin glass combined with the carrier, the thermal, vacuum, solvent, and acidic and ultrasonic Flat Panel Display (FPD) processes require a secure bond. FPD processes typically involve vacuum deposition (sputtering metals, transparent conductive oxides and oxide semiconductors; chemical vapor deposition (CVD) amorphous germanium, tantalum nitride and germanium dioxide; and dry etching of metals and insulators) , thermal process (including CVD deposition of about 300 ° C to 400 ° C, p-Si crystallization up to 600 ° C, oxide semiconductor annealing of 350 ° C to 450 ° C, dopant annealing up to 650 ° C and about 200 ° C to 350 ° C Contact annealing), acid etching (metal etching, oxide semiconductor etching), solvent exposure (stripping photoresist, deposition polymer encapsulation) and ultrasonic exposure (in solvent stripping photoresist and water purification, usually In an alkaline solution).

Adhesive wafer bonding has been widely used in micro-machinery systems (MEMS) and in semiconductor processing where the process is less critical. Adhesives marketed by Brewer Science and Henkel are typically thick polymer adhesion layers from 5 microns to 200 microns thick. Such The greater thickness of the layer allows for the presence of large amounts of volatile materials, trapped solvents, and adsorbed species to contaminate the FPD process. These materials thermally decompose and outgas at temperatures above about 250 °C. Such materials may also be contaminated by acting as a reservoir of gases, solvents, and acids in a downstream step that may be released during subsequent processing.

Title application of the 2012 February 8 for the Processing Flexible Glass with a Carrier of US Provisional Application No. 61 / 596,727 (hereinafter, US '727) discloses the following concepts: which involves initially by van der Waals force (van Der Waals forces) joining a sheet (eg, a flexible glass sheet) to a carrier, and subsequently increasing the bond strength in certain areas while maintaining the sheet/carrier in processing to form an element on the sheet/carrier (eg, Removing an electronic component or a display component, a component of the electronic component or display component, an organic light emitting device (OLED) material, a photo-voltaic (PV) structure, or a thin film transistor ability. Bonding at least a portion of the thin glass to the carrier to prevent component process fluid from entering between the wafer and the carrier, thereby reducing the probability of contamination of the downstream process, ie, the joint sealing portion between the sheet and the carrier is gas The seal, and in some preferred embodiments, encloses the exterior of the article to prevent intrusion or intrusion of liquid or gas into any area of the article of sealing.

US '727 continues to reveal that in low temperature polysilicon (LTPS) (low temperature compared to solid phase crystallization, solid phase crystallization can be as high as about 750 ° C) component manufacturing process, can be used close to 600 ° C or above 600 ° C Temperature, vacuum and wet etching environments. These conditions limit the materials that can be used and place higher demands on the carrier/sheet. What is needed, therefore, is a carrier method that utilizes the manufacturer's existing capital infrastructure that enables the processing of thin glass (i.e., thickness) at higher processing temperatures. 0.3 mm thick glass) without contaminating or losing the joint strength between the thin glass and the carrier, and wherein the thin glass is easily disengaged from the carrier at the end of the process.

A commercial advantage of the method disclosed in US '727 is that, as indicated in US '727, manufacturers will be able to utilize their existing capital infrastructure processing equipment while obtaining, for example, PV, OLED, LCD and patterned thin film electricity. The advantage of a thin glass sheet of crystalline (Thin Film Transistor, TFT) electronic components. In addition, the method provides flexibility in the process, including: cleaning and surface pre-treatment of thin glass sheets and carriers to facilitate bonding; strengthening the bond between the sheet and the carrier at the joint area; maintaining non-engagement (or lowering/lowering) The strength of the sheet is detachable from the carrier at the region of the strength; and the sheet is cut to facilitate extraction from the carrier.

In a glass-to-glass bonding process, the glass surface is cleaned to remove all metal, organic, and particulate residues and leave a surface that is primarily terminated with decyl alcohol. The glass surfaces are first brought into intimate contact, wherein the van der Waals bonding and/or hydrogen bonding forces attract the glass surfaces together. The surface stanol groups condense in the presence of heat and optionally pressure to form strong covalent Si-O-Si bonds across the interface to permanently fuse the glass sheets. Metal, organic, and particulate residues will interfere with the joint by masking the surface, which obstructs the intimate contact required for the joint. The high stanol surface concentration is also required to form a strong bond because the number of bonds per unit area will be determined by the probability of condensation of water out of the reaction of the two stanol species on the opposite surface. Zhuravlel has reported that for fully hydrated cerium oxide, the average number of hydroxyl groups per nm ² is 4.6 to 4.9. Zhuravlel, LT, The Surface Chemistry of Amorphous Silika, Zhuravlev Model, Colloids and Surfaces A: Physiochemical Engineering Aspects 173 (2000) 1-38. In US '727, a non-joining region is formed within the joint perimeter, and the primary manner described with respect to forming such a non-joining region is to increase surface roughness. An average surface roughness greater than 2 nm Ra prevents the formation of a glass-to-glass bond during the high temperature bonding process. In filed on December 13, 2012 by the same inventors and entitled Facilitated Processing for Controlling Bonding Between Sheet and of U.S. Provisional Application No. 61 / 736,880 Carrier (hereinafter, US '880), the control by the carrier The van der Waals bonding and/or hydrogen bonding with the thin glass sheets forms a controlled joint region, while still using a covalently bonded region. Thus, while the articles and methods used to process sheets and carriers in US '727 and US '880 can withstand harsh FPD processing environments that are not ideal for some applications, but by covalent (eg, Si-O-Si) In the joint region where the bonding force of about 1000 mJ/m ² to 2000 mJ/m ² (about the breaking strength of the glass) is bonded, strong covalent bonding between the thin glass and the glass carrier hinders reuse of the carrier. The swaying or peeling cannot be used to separate the covalently bonded portion of the thin glass from the carrier, and thus the entire sheet cannot be removed from the carrier. Instead, the non-joined areas with the elements thereon are scribed and drawn to leave the bonded perimeter of the thin glass sheets on the carrier.

In light of the above, there is a need for a wafer carrier article that can withstand high temperature processing (there is no outgassing that would be incompatible with semiconductor or display manufacturing processes, which would be used in semiconductor or display manufacturing processes) Objects) and other harsh FPD processing conditions, while allowing the entire sheet area (together or sub-portion) to be removed from the carrier to allow the vehicle to be reused for processing another Sheet. This specification describes a manner for controlling the adhesion between the carrier and the sheet to create a temporary joint that is strong enough to withstand FPD processing (including LTPS processing) but weak enough to allow the sheet to be Disengagement from the carrier, even after high temperature processing. Such controlled bonding can be used to fabricate articles having reusable carriers, or articles having controlled engagement and covalently bonded patterned regions between the carrier and the sheet. More particularly, the present invention provides a surface modifying layer (including various materials and associated surface heat treatments) that can be disposed on the sheet, the carrier, or both to control the sheet and the carrier. The room temperature between the van der Waals bonding and/or hydrogen bonding is covalently bonded to the high temperature. Even more specifically, room temperature bonding can be controlled to hold the sheet together with the carrier during vacuum processing, wet processing, and/or ultrasonic cleaning processes. And at the same time, high temperature covalent bonding can be controlled to prevent permanent bonding between the sheet and the carrier during high temperature processing, as well as to maintain bonding sufficient to prevent delamination during high temperature processing. In alternative embodiments, the surface modifying layers can be used to fabricate a variety of controlled joining regions (where the carrier and the sheet remain fully joined via various processes, including vacuum processing, wet processing, and/or ultrasonic cleaning) And covalently bonded regions to provide other processing options, such as maintaining a gas density between the carrier and the sheet, even after the article has been cut into smaller pieces for additional component processing. In addition, some surface modifying layers can control the bonding between the carrier and the sheet while reducing outgassing during harsh conditions in an FPD (eg, LTPS) processing environment, including, for example, high temperature and/or vacuum processing. .

Other features and advantages will be set forth in the description which follows. Some of the features and advantages are recognized in the written description and the various aspects illustrated in the drawings. The above general description and the following detailed description are merely illustrative of the embodiments of the invention

The drawings are included to provide a further understanding of the concepts of the invention, and are incorporated in this specification and constitute a part of this specification. The drawings illustrate one or more embodiments and, together with the description It should be understood that the various features disclosed in the specification and drawings can be used in any and all combinations. As a non-limiting example, various features may be combined with each other as described in the appended claims.

2‧‧‧glass objects

8‧‧‧Thickness of glass objects

10‧‧‧ Vehicles

14‧‧‧ joint surface

20‧‧‧Sheet

26‧‧‧The periphery of the sheet

28‧‧‧Sheet thickness

30‧‧‧ Surface modification layer

38‧‧‧The thickness of the surface modification layer

40‧‧‧ joint area

50‧‧‧Controlled joint area

52‧‧‧The perimeter of the controlled joint area

56‧‧‧ required parts

Surroundings of the required parts of 57‧‧

900‧‧‧ Vehicles

902‧‧‧ surface

910‧‧‧ Covering

912‧‧‧ Covering surface

920‧‧‧ spacers

930‧‧‧室

940‧‧‧Indicating the direction of N2 gas flow

Figure 1 is a schematic side elevational view of an article having a carrier joined to a sheet by a surface modifying layer interposed between the carrier and the sheet.

Fig. 2 is an exploded and partial cross-sectional view of the object in Fig. 1.

Figure 3 is a graph of the concentration of surface hydroxyl groups on cerium oxide as a function of temperature.

Figure 4 is a graph of the surface energy of a SC1 cleaned glass sheet as a function of annealing temperature.

Figure 5 is a graph showing the percentage change in the surface energy of a fluoropolymer film deposited on a glass sheet as a function of one of the constituent materials of the film.

Figure 6 is a schematic plan view of the sheet being joined to the carrier by the joint region.

Figure 7 is a schematic view of the test device.

Figure 8 is a collection of graphs of surface energy versus time for various materials under different conditions (different portions of the test apparatus of Figure A).

Figure 9 is a graph of percent change in bubble area versus temperature for various materials.

Figure 10 is another graph of percent change in bubble area versus temperature for various materials.

In the following detailed description, example embodiments of the invention are in the It will be apparent, however, that the invention may be practiced in other embodiments of the specific embodiments disclosed herein. In addition, descriptions of well-known elements, methods, and materials may be omitted to avoid obscuring the description of the various concepts of the invention. Finally, the same component symbols refer to the same components, wherever applicable.

Ranges may be expressed herein as "about" a particular value and/or to "about" another particular value. When such a range is indicated, another embodiment includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, the use of the It should be further understood that the endpoint of each range is clearly associated with both the other endpoint and the other endpoint.

Directional terms as used herein, such as up, down, right, left, front, back, top, bottom, are only given with reference to the figures, and are not intended to imply absolute orientation.

As used herein, unless the context clearly dictates otherwise, the singular The forms "a/an" and "the" include plural indicators. Thus, for example, reference to "a component" includes the aspect of having two or more such components, unless the context clearly dictates otherwise.

In both US '727 and US '880, a solution is provided that allows processing of a thin glass sheet on a carrier whereby at least a portion of the thin glass sheet remains "non-joined" so that the components processed on the thin glass sheet Can be removed from the vehicle. However, the periphery of the thin glass is permanently (or covalently, or hermetically) bonded to the carrier glass by forming covalent Si-O-Si bonds. The perimeter of the covalent bond prevents reuse of the carrier because the thin glass in the permanent land cannot be removed without damaging the thin glass and the carrier.

To maintain advantageous surface shape characteristics, the carrier is typically a display grade glass substrate. Therefore, in some cases, it is wasteful and expensive to dispose of the carrier only after one use. Therefore, in order to reduce the manufacturing cost of the display, it is necessary to be able to use the carrier to process more than one sheet substrate. The present invention sets forth the following objects and methods that enable the processing of sheets in the harsh environment of an FPD processing line, including harsh processing, where high temperature processing is Processing at a temperature of 400 ° C and depending on the type of component being fabricated, for example, in an amorphous germanium or amorphous indium gallium zinc oxide (IGZO) backsheet treatment, the temperature is up to about 450 ° C, in crystallization Up to about 500 ° C to 550 ° C in IGZO processing, or up to about 600 ° C to 650 ° C in LTPS processes, while still allowing no damage (for example, where the carrier and one of the sheets break or break into two pieces) In the case of the sheet or the carrier, the sheet is easily removed from the carrier, whereby the carrier can be reused.

As shown in Figures 1 and 2, the glass article 2 has a thickness of 8 and comprises a carrier 10 having a thickness 18, a sheet 20 having a thickness 28 (i.e., thickness) 300 micron lamellae, including but not limited to, for example, 10 micrometers to 50 micrometers, 50 micrometers to 100 micrometers, 100 micrometers to 150 micrometers, 150 micrometers to 300 micrometers, 300 micrometers, 250 micrometers, 200 micrometers, 190 micrometers, 180 micrometers 170, 160, 150, 140, 130, 120, 110, 100, 90, 80, 70, 60, 50, 40, 30, 20 or 10 The thickness of the micron) and the surface modifying layer 30 having a thickness of 38. The glass article 2 is designed to allow for thicker sheets (ie, about The sheet 20 is processed in a 0.4 mm sheet, such as a 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm or 1.0 mm design, but the sheet 20 itself 300 microns. That is, the thickness 8 as the sum of the thicknesses 18, 28, and 38 is designed to be equivalent to the thickness of the thicker sheet, and a processing apparatus is designed for the thicker sheet (eg, designed to use electronic component assemblies) Equipment placed on the substrate sheet). For example, assuming a thickness of 38 is negligible, if the processing apparatus is designed for a 700 micron sheet and the thickness 28 of the sheet is 300 microns, the thickness 18 will be chosen to be 400 microns. That is, the surface modifying layer 30 is not shown to scale; rather, it is greatly enlarged for the sake of explanation. In addition, the surface modifying layer is shown in a sectional view. In fact, when a reusable carrier is provided, the surface modifying layer will be evenly disposed on the joining surface 14. Typically, the thickness 38 will be on the order of a few nanometers, such as 0.1 nm to 2.0 nm or as much as 10 nm, and in some cases up to 100 nm. This thickness 38 can be measured by an ellipsometer. Alternatively, the presence of a surface modifying layer can be detected by surface chemical analysis, such as by ToF Sims mass spectrometry. Thus, the contribution of thickness 38 to article thickness 8 is negligible and the contribution of thickness 38 can be neglected when calculating to determine a suitable thickness 18 for processing carrier 10 having a specified thickness 20 of thickness 28. However, to the extent that the surface modifying layer 30 has any significant thickness 38, this thickness can be taken into account when determining the thickness 18 of the carrier 10 for a specified thickness 28 of the sheet 20, and the processing apparatus is designed for a specified thickness.

The carrier 10 has a first surface 12, an engagement surface 14, a perimeter 16 and a thickness 18. Additionally, the carrier 10 can have any suitable material including, for example, glass. The carrier need not be glass, but instead may be ceramic, glass-ceramic or metal (since the surface energy and/or bonding can be controlled in a manner similar to that described below in connection with the glass carrier). If made of glass, the carrier 10 can have any suitable composition, including aluminosilicate, borosilicate, aluminoboronate, soda lime citrate, and may or may not contain an alkali depending on the final application. . The thickness 18 can be from about 0.2 mm to 3 mm or more, such as 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.65 mm, 0.7 mm, 1.0 mm, 2.0 mm, or 3 mm or more, and will be as above The apparent thickness 28 and thickness 38 (when thickness 38 is not negligible). Additionally, the carrier 10 can be comprised of one layer (as shown) or a plurality of layers joined together (including a plurality of sheets). Further, the carrier may be of a size of 1 or greater, such as Gen 2, Gen 3, Gen 4, Gen 5, Gen 8, or larger (for example, a sheet size of 100 mm × 100 mm to 3 m × 3 m or more) Big).

The sheet 20 has a first surface 22, a joint surface 24, a perimeter 26, and a thickness 28. The perimeters 16 and 26 can have any suitable shape, can be identical to one another, or can be different from one another. Additionally, the sheet 20 can have any suitable material including, for example, glass, ceramic or glass-ceramic. When made from glass, thin 20 may have any suitable composition, including aluminosilicates, borosilicates, aluminoboronates, soda limes, and may or may not contain a base, depending on the end use. The thermal expansion coefficient of the sheet can be relatively closely matched to the coefficient of thermal expansion of the carrier to prevent the article from warping at high temperatures during processing. As described above, the thickness 28 of the sheet 20 is 300 microns or less. Further, the sheet may have a size of Gen 1 or larger, such as Gen 2, Gen 3, Gen 4, Gen 5, Gen 8, or larger (for example, a sheet size of 100 mm × 100 mm to 3 m × 3 m or more) .

The article 2 not only needs to have the correct thickness for handling in existing equipment, but will also need to be able to withstand the harsh environments of processing. For example, flat panel display (FPD) processing can include wet ultrasonic, vacuum, and high temperature (eg, 400 ° C) treatment. For some processes, as described above, the temperature can be 500 ° C, or 600 ° C, and up to 650 ° C.

To withstand the harsh environment in which the article 2 will be handled, such as during FPD fabrication, the engagement surface 14 should be joined to the engagement surface 24 with sufficient strength to prevent the sheet 20 from separating from the carrier 10. This strength should be maintained throughout the process so that the sheet 20 does not separate from the carrier 10 during processing. Moreover, to allow removal of the sheet 20 from the carrier 10 (so that the carrier 10 can be reused), the bonding surface 14 should not be modified by the originally designed bonding force and/or by the bonding force that may have occurred from the original design. And the resulting bonding force (for example, when the object is at a high temperature (for example When the treatment is carried out at a temperature of 400 ° C), the bonding surface 24 is excessively bonded. Surface modification layer 30 can be used to control the bond strength between joint surface 14 and joint surface 24 to achieve both of these goals. The controlled bonding force is achieved by controlling the contribution of van der Waals bonding (and/or hydrogen bonding) and covalent attraction energy to the total adhesion energy by adjusting the polarity and non-polarity of the sheet 20 and the carrier 10. The surface energy component is controlled. This controlled joint is strong enough to withstand FPD processing (including wet, ultrasonic, vacuum, and thermal processes, including 400 ° C temperature and in some cases including 500 ° C or The processing temperature of 600 ° C and up to 650 ° C) is maintained by the application of sufficient separation force and by the force that does not cause catastrophic damage to the sheet 20 and/or the carrier 10 . Such disengagement allows removal of the sheet 20 and the components fabricated on the sheet, and also allows reuse of the carrier 10.

Although the surface modifying layer 30 is shown as being in the form of a solid layer between the sheet 20 and the carrier 10, this is not necessarily the case. For example, layer 30 can be about 0.1 nm to 2 nm thick and does not necessarily completely cover every point of bonding surface 14. For example, the coverage rate can be 100%, 1% to 100%, 10% to 100%, 20% to 90% or 50% to 90%. In other embodiments, layer 30 may be as thick as 10 nm thick, or even as much as 100 nm thick in other embodiments. The surface modifying layer 30 can be considered to be disposed between the carrier 10 and the sheet 20, but the surface modifying layer does not necessarily contact one or the other of the carrier 10 and the sheet 20. In any event, an important aspect of the surface modifying layer 30 is that the surface modifying layer can improve the ability of the bonding surface 14 to engage the bonding surface 24 to control the bond strength between the carrier 10 and the sheet 20. The material and thickness of the surface modifying layer 30 and the pre-bonding bonding surfaces 14, 24 can be used to control the bond strength (adhesion energy) between the carrier 10 and the sheet 20.

In general, the adhesion between the two surfaces can be provided by ("A theory for the estimation of surface and interfacial energies. I. derivation and application to interfacial tension", LA Girifalco and RJ Good, J. Phys. Chem. , vol. 61, p. 904): W = γ ₁ + γ ₂ - γ ₁₂ (1)

Wherein γ ₁ , γ ₂ and γ ₃ are the surface energy of the surface 1, the surface 2 and the interface energy of the surfaces 1 and 2, respectively. Individual surface energies are usually a combination of two components: the dispersion component γ ^d and the polar component γ ^p : γ = γ ^d + γ ^p (2).

When adhesion is primarily attributed to London dispersion forces (γ ^d ) and polar forces (eg hydrogen bonding) (γ ^p ), the interfacial energy can be provided by the following formula (Girifalco and RJGood, as mentioned above):

After substituting (3) into (1), the adhesion energy can be approximated as:

In the above equation (4), only the van der Waals bonding (and/or hydrogen bonding) component of the adhesion energy is considered. These components include polar-polar interactions (Keesom), polar-nonpolar interactions (Debye), and non-polar-nonpolar interactions (London). However, other attractive energies may also be present, such as covalent bonding and electrostatic bonding. Therefore, in a more general form, write the above equation:

Where w _c and w _e are covalent adhesion energy and electrostatic adhesion energy. Covalent adhesion can be quite common, as in tantalum wafer bonding, where the preliminary hydrogen bonded wafers are heated to a higher temperature to convert most or all of the stanol-stanol hydrogen bonds to Si-O-Si. Covalent bond. Although the initial room temperature hydrogen bonding produces an adhesion energy of from about 100 mJ/m ² to about 200 mJ/m ² , the adhesion allows separation of the bonded surface, but complete covalent bonding achieved during high temperature processing (about 400 ° C to 800 ° C). The paired wafers have an adhesion energy of about 1000 mJ/m ² to 3000 mJ/m ² , which does not allow separation of the bonded surfaces; rather, the two wafers act as a unit. On the other hand, if both surfaces are completely coated with a low surface energy material (e.g., a fluoropolymer) at a thickness sufficient to shield the effect of the underlying substrate, the adhesion energy will be the adhesion of the coating material and will be extremely low, Thereby a low or no adhesion occurs between the joining surfaces 14, 24, whereby the sheet 20 will not be able to be processed on the carrier 10. Consider two extreme cases: (a) two standard cleaning 1 (SC1, known in the art) cleaned glass surfaces saturated with stanol groups bonded together via hydrogen bonding at room temperature (by adhering thereto) It can be from about 100 mJ/m ² to 200 mJ/m ² ) and then heated to a high temperature, thereby converting the stanol group into a covalent Si—O—Si bond (by which the adhesion energy can be changed from 1000 mJ/m ² to 3000 mJ/ m ² ). Thereafter, one of the adhesions is so high that the pair of glass surfaces are not detachable; and (b) the two glass surfaces completely coated with the low surface adhesion fluoropolymer (about 12 mJ/m ² per surface) are joined at room temperature. And heated to a high temperature. The surfaces are not joined in this latter case (b) (because the total adhesion energy of about 24 mJ/m ² is too low when the surfaces are put together), and they are not joined at high temperatures because they do not exist ( Or too little) polar reactive groups. Between these two extremes, there is an range of adhesion energy, such as an adhesion energy between 50 mJ/m ² and 1000 mJ/m ² , which can produce a desired degree of controlled bonding. Accordingly, the inventors have discovered that various ways of providing the surface modifying layer 30 create an adhesion energy between these two extremes and that a controlled bond can be created that is sufficient to maintain a pair of glass substrates (eg, The glass carrier 10 and the thin glass sheet 20) are joined to each other under severe FPD processing conditions and the degree of bonding (even if, for example, After the high temperature treatment at 400 ° C), the sheet 20 is allowed to detach from the carrier 10 after the treatment is completed. In addition, the sheet 20 and the carrier 10 can be separated by mechanical force, and in this way at least catastrophic damage to the sheet 20 is not caused, and preferably the carrier 10 is not catastrophically damaged.

Equation (5) describes the adhesion energy as a function of the four surface energy parameters plus covalent energy and electrostatic energy, if any.

The proper adhesion can be achieved by careful selection of the surface modifying agent (i.e., surface modifying layer 30) and/or by heat treating the surface prior to bonding. Appropriate adhesion energy can be obtained by selecting a chemical modifier that bonds one or both of the surface 14 and the bonding surface 24, which in turn controls the van der Waals bonding (and/or hydrogen bonding, as these terms are in Adhesive energy is used interchangeably in the instructions and is handled by high temperatures (for example, approximately 400 ° C) produces the possible covalent bond adhesion energy. For example, obtaining the bonding surface of the SC1 cleaning glass (which is initially saturated with stanol groups to have a high polarity component of surface energy) and coating the bonding surface with a low energy fluoropolymer to control polar and non-polar groups The local coverage of the group on the surface. This not only controls the initial van der Waals (and/or hydrogen) junction at room temperature, but also controls the degree of covalent bonding/degree at higher temperatures. Controlling the initial van der Waals (and/or hydrogen) bonding at room temperature to provide a surface to bond with another surface to allow for vacuum and/or spin-flush-dry (SRD) type processing, and in some cases also An easily formed joint of one surface with another surface, wherein the easily formed joint can be performed at room temperature without applying an externally applied force to the entire area of the sheet 20, as with a squeegee or a reduced pressure environment This is performed when the sheet 20 is pressed to the carrier 10. That is, the initial Van der Waals joint provides at least a minimum degree of engagement to hold the sheet together with the carrier such that if one is held to allow the other to withstand gravity, the sheet and carrier are not separated. In most cases, the initial van der Waals (and/or hydrogen) bond will be as follows: the article can also be subjected to vacuum, SRD and ultrasonic treatment without delamination of the sheet and carrier. Heat treating the bonding via the surface modifying layer 30 (including the surface treatment of the surface from which the surface modifying layer is made and/or the surface to which the surface modifying layer is applied) and/or by joining the joining surfaces together The surface precisely controls both van der Waals bonding (and/or hydrogen bonding) and covalent interactions to an appropriate degree, thereby achieving the desired adhesion energy, which allows the sheet 20 and the carrier 10 to be processed throughout the FPD type. The middle join while allowing the sheet 20 to be separated from the carrier 10 after FPD type processing (by appropriate force, thereby avoiding damage to the sheet 20 and/or the carrier). Additionally, where appropriate, an electrostatic charge can be applied to one or both of the glass surfaces to provide another degree of control of the adhesion energy.

FPD processing (eg, p-Si and oxide TFT fabrication) typically involves a thermal process at temperatures above 400 ° C, above 500 ° C, and in some cases at or above 600 ° C, up to 650 ° C in the absence of surface modification. In the case of layer 30, the thermal processes can cause glass-glass bonding of thin glass sheet 20 to glass carrier 10. Controlling the formation of the Si-O-Si bond thus results in a reusable carrier. One method of controlling the formation of Si-O-Si bonding at elevated temperatures is to reduce the concentration of surface hydroxyl groups on the surface to be bonded.

As shown in Fig. 3, the graph is an Iler's plot of surface hydroxyl concentration on cerium oxide as a function of temperature (RKIller: The Chemistry of Silica (Wiley-Interscience, New York, 1979). )), the number of hydroxyl groups (OH groups) per square nanometer decreases as the surface temperature increases. because However, heating the cerium oxide surface (and the like, such as bonding surface 14 and/or bonding surface 24) can reduce the concentration of surface hydroxyl groups, thereby reducing the chance that the hydroxyl groups on the two glass surfaces will interact. This reduction in surface hydroxyl concentration reduces the Si-O-Si bond formed per unit area, thereby reducing adhesion. However, the elimination of surface hydroxyl groups requires a longer annealing time at elevated temperatures (above 750 ° C to completely eliminate surface hydroxyl groups). Such longer annealing times and higher annealing temperatures make the process more expensive and impractical because it may be higher than the strain point of a typical display glass.

Based on the above analysis, the inventors have found that an article including a sheet and a carrier and suitable for FPD processing (including LTPS processing) can be manufactured by weighing the following three concepts: (1) modifying the initial room temperature bonding to modify the loading With and/or a sheet joining surface, this control can be performed by controlling the van der Waals (and/or hydrogen) bonding to produce a medium adhesion energy (eg, a surface energy of >40 mJ/m ² per surface prior to surface bonding). ) to facilitate initial room temperature bonding and sufficient to withstand non-high temperature FPD processes, such as vacuum processing, SRD processing, and/or ultrasonic processing; (2) surface modification of the carrier and/or sheet in a thermally stable manner so as to Sustaining the FPD process without outgassing, which may result in delamination and/or unacceptable contamination during component fabrication, for example, for semiconductor and/or display manufacturing processes where the article may be used Accepted contamination; and (3) control of bonding at elevated temperatures, which can be controlled by controlling the surface hydroxyl concentration of the carrier and at elevated temperatures (eg, temperature) 400 ° C) is carried out at a concentration of other substances capable of forming a strong covalent bond, whereby the bonding energy between the bonding surface of the carrier and the bonding surface of the sheet can be controlled, so that even at high temperatures (especially via After a thermal process in the range of 500 ° C to 650 ° C, as in the FPD process, the adhesion between the carrier and the sheet is maintained within a range that allows the separation of the sheet from the carrier with a certain separation force. The separation force does not damage the sheet at least (and preferably does not damage the sheet or the carrier) and is sufficient to maintain the engagement between the carrier and the sheet such that the carrier and the sheet do not delaminate during processing .

Furthermore, the inventors have discovered that the use of the surface modifying layer 30 and, where appropriate, the bonding surface pretreatment, provides a balance between the above concepts in order to easily achieve a controlled joint area, i.e., between the sheet 20 and the carrier 10. Providing sufficient room temperature bonding to allow handling of the article 2 in an FPD type process (including vacuum and wet processes) while controlling covalent bonding between the sheet 20 and the carrier 10 (even in At a high temperature of 400 ° C) to allow removal of the sheet 20 from the carrier 10 after the article 2 has completed high temperature processing (eg, FPD type processing or LTPS processing) (at least without damaging the sheet, and preferably without damaging the carrier) The joint area of ). To evaluate potential joint surface pretreatment and surface modification layers that would provide a reusable carrier suitable for FPD processing, a series of tests were used to assess their suitability. Different FPD applications have different requirements, but the LTPS and oxide TFT processes appear to be the most stringent at this time, and thus the tests representing the steps in such processes are selected because these processes are the applications of the object 2. Vacuum processes, wet cleaning (including SRD and ultrasonic processes) and wet etching are common for many FPD applications. Typical aSi TFT fabrication requires processing at up to 320 °C. Annealing at 400 ° C is used in the oxide TFT process, while in the LTPS process, the crystallization and dopant activation steps performed above 600 ° C are used. Therefore, using the following five tests to evaluate a particular joint surface pretreatment and surface modification layer 30 would allow the sheet 20 to remain engaged with the carrier 10 throughout the FPD process while allowing for such processing (including at temperature). The possibility of removing the sheet 20 from the carrier 10 (without damaging the sheet 20 and/or the carrier 10) after treatment at 400 °C). These tests are performed in sequence, and the sample proceeds from one test to the next, unless there is a failure type that will not allow subsequent testing.

(1) Vacuum test. Vacuum compatibility test was performed in an STS Multiplex PECVD vacuum lock (available from SPTS, Newport, UK) by an Ebara A10S dry pump with a soft pump valve (available from Ebara Technologies Inc., Sacramento, CA) Suction the vacuum lock. The sample was placed in the vacuum lock and the vacuum lock was then pumped from atmospheric pressure to 70 mTorr in 45 seconds. If the following conditions exist, it is considered that the failure in the "vacuum" line of the following table indicated by the mark "F" has occurred: (a) the adhesion between the carrier and the sheet is lost (by visual inspection with the naked eye, If the sheet is detached from the carrier or disengaged from the carrier portion, it is considered to have failed; (b) bubbling occurs between the carrier and the sheet (as determined by visual inspection with the naked eye: photographing the sample before and after treatment, Subsequent comparisons, if the size of the defect is increased to the naked eye, it is determined that a failure has occurred; or (c) the sheet is moved relative to the carrier (as determined by visual observation with the naked eye: the sample is taken before and after the test) Photographing in which a joint defect (such as a bubble) moves, or if the edge is disengaged, or if the sheet moves over the carrier, it is considered to have failed. In the table below, the mark "P" in the "vacuum" line indicates that the sample is not failed according to the above criteria.

(2) Wet Process Test. Wet process compatibility test was performed using a Semitool model SRD-470S (available from Applied Materials, Santa Clara, CA). The test consisted of rushing at 500 rpm under a stream of warm nitrogen. After washing for 60 seconds, it was rinsed to 15 MΩ-cm at 500 rpmQ, purged at 500 rpm for 10 seconds, dried at 1800 rpm for 90 seconds, and dried at 2400 rpm for 180 seconds. If the following conditions exist, it is considered that the failure of the "SRD" line in the following table indicated by the mark "F" has occurred: (a) the adhesion between the carrier and the sheet is lost (by visual inspection with the naked eye, Wherein if the sheet is detached from the carrier or disengaged from the carrier portion, it is considered to have failed; (b) bubbling occurs between the carrier and the sheet (as determined by visual inspection with the naked eye: photographing the sample before and after treatment) And then comparing, if the size of the defect is increased to the naked eye, it is determined that the failure has occurred; or (c) the movement of the sheet relative to the carrier (as determined by visual observation with the naked eye: before and after the test) Sample photographing in which if a joint defect (such as a bubble) moves, or if the edge is disengaged, or if the sheet moves over the carrier, it is considered to have failed; or (d) water penetrates under the sheet (eg, by using an optical microscope) Determined by visual inspection at 50x, where if a liquid or residue is observable, it is determined that a failure has occurred. In the table below, the mark "P" in the "SRD" line indicates that the sample is not failed according to the above criteria.

(3) Test at a temperature of 400 ° C. A 400 ° C process compatibility test was performed using an Alwin 21 Accuthermo 610 RTP (available from Alwin 21, Santa Clara, CA). The carrier bonded to the sheet was heated in a chamber which was circulated from room temperature to 400 ° C at 6.2 ° C/min, held at 400 ° C for 600 seconds, and cooled to 300 ° C at 1 ° C/min. The carrier and sheet are then allowed to cool to room temperature. If the following conditions exist, it is considered that the "400 ° C" line in the following table has failed as indicated by the mark "F": (a) the adhesion between the carrier and the sheet is lost (by visual inspection with the naked eye) Where, if the sheet is detached from the carrier or disengaged from the carrier portion, it is considered that a failure has occurred; (b) bubbling occurs between the carrier and the sheet (as determined by visual inspection with the naked eye: before and after treatment) Photographing the sample, and then comparing, if the size of the defect is increased to the naked eye, it is determined that the failure has occurred; or (c) the adhesion between the carrier and the sheet is enhanced, whereby the adhesion is enhanced without damage to the carrier sheet or the carrier sheet to prevent disengagement (by inserting a razor blade between the sheet and the carrier, and / or by the a 1 "wide × 6" length of the Kapton ^TM tape sticks Sheet and pull the tape, where 2" to 3" tape is attached to a 100mm ² thin glass (K102 series from Saint Gobain Performance Plastic (Hoosik, NY)), where the sheet or carrier is used when attempting to separate the sheet from the carrier There is damage, or if it is not possible to perform any release In the method of disengaging the sheet from the carrier, it is considered that a failure has occurred. Additionally, the debonding test is performed on a representative sample after the sheet is bonded to the carrier and prior to thermal cycling to determine that the particular material (including any associated surface treatment) does allow disengagement of the sheet from the carrier prior to temperature cycling. In the table below, the mark "P" in the "400 ° C" line indicates that the sample is not failed according to the above criteria.

(4) Test at a temperature of 600 ° C. The 600 ° C process compatibility test was performed using an Alwin 21 Accuthermo 610 RTP. The carrier and the sheet were heated in a chamber cooled at 9.5 ° C/min from room temperature to 600 ° C, held at 600 ° C for 600 seconds, and then cooled to 300 ° C at 1 ° C/min. The carrier and sheet are then allowed to cool to room temperature. If the following conditions exist, it is considered that the "600 ° C" line in the following table has failed as indicated by the mark "F": (a) the adhesion between the carrier and the sheet is lost (by visual inspection with the naked eye) Where, if the sheet is detached from the carrier or disengaged from the carrier portion, it is considered to have failed; (b) bubbling occurs between the carrier and the sheet (as determined by visual inspection with the naked eye: the sample is taken before and after treatment) Photographing, and then comparing, if the size of the defect is increased to the naked eye, it is determined that a failure has occurred; or (c) the adhesion between the carrier and the sheet is enhanced, whereby the adhesion is enhanced without damage where the carrier sheet or the carrier sheet to prevent disengagement (by inserting a razor blade between the sheet and the carrier, and / or as described above by the Kapton ^TM tape of a sheet sticks and pulling on the tape, If the sheet or the carrier is damaged when attempting to separate the sheet from the carrier, or if the sheet cannot be disengaged from the carrier by performing any disengagement method, it is considered that a failure has occurred. In addition, the sheet is engaged with the carrier. After and in the heat Prior to cycling, a representative sample was subjected to a debonding test to determine that the particular material and any associated surface treatments did allow the sheet to be disengaged from the carrier prior to temperature cycling. In the table below, the "P" indication in the "600 °C" row is indicated. According to the above criteria, the sample did not pass.

(5) Ultrasonic test. Ultrasonic compatibility test was carried out by cleaning the object in a four-slot line, wherein the object was processed in each of the slots from the first to the fourth grooves. For each of the four tanks, the tank size is 18.4" long x 10" wide by 15" deep. The two cleaning tanks (No. 1 and No. 2) contain 1% Semiclean KG (available from Yokohama Oils and 50 ° C DI water from Fats Industry Co Ltd., Yokohama, Japan) Stir No. 1 cleaning tank with NEY prosonik 2 104 kHz ultrasonic generator (available from Blackstone-NEY Ultrasonics, Jamestown, NY) with NEY prosonik 2 104 kHz The ultrasonic generator agitates the No. 2 cleaning tank. The two flushing tanks (No. 3 and No. 4) contain 50 °C DI water. The No. 3 flushing tank is stirred by the NEY sweepsonik 2D 72kHz ultrasonic generator and borrowed. Stir the No. 4 rinse tank by NEY sweepsonik 2D 104kHz ultrasonic generator. In slot 1 to These processes were carried out for 10 minutes in each of the No. 4 tanks, followed by spin rinse drying (SRD) after removing the sample from the No. 4 tank. If the following conditions exist, it is considered that the "supersonic" line in the following table has failed due to the mark "F": (a) the adhesion between the carrier and the sheet is lost (by visual inspection with the naked eye) Where, if the sheet is detached from the carrier or disengaged from the carrier portion, it is considered that a failure has occurred; (b) bubbling occurs between the carrier and the sheet (as determined by visual inspection with the naked eye: before and after treatment) Photographing the sample, and then comparing, if the size of the defect is increased to the naked eye, it is determined that a failure has occurred; or (c) forming other significant defects (eg, by visual inspection at 50× with an optical microscope) Determining that if there is a previously unobserved capture particle between the thin glass and the carrier, it is considered that a failure has occurred; or (d) the water penetrates under the sheet (eg, by visual inspection at 50× with an optical microscope) It is determined that if a liquid or residue is observable, it is determined that a failure has occurred. In the table below, the mark "P" in the "Ultrasonic" line indicates that the sample is not failed according to the above criteria. Also, in the table below, the blank in the "Ultrasonic" line indicates that the sample was not tested in this way.

Bonding surface treatment by reducing hydroxyl groups by heating

One or more of the bonding surfaces 14, 24 are modified with the surface modifying layer 30 to enable the article 2 to successfully perform FPD processing (i.e., wherein the sheet 20 remains engaged with the carrier 10 during processing, while still being processed The benefit of separating from the carrier 10 (including the high temperature treatment) is treated by having the glass carrier 10 and the thin glass sheet 20 without the surface modifying layer 30 between the glass carrier 10 and the thin glass sheet 20. Object 2 to prove. Specifically, first by heating to reduce the hydroxyl group but in the absence of the surface modifying layer 30, try to The joining surfaces 14, 24 are pretreated. The carrier 10 and the sheet 20 are cleaned so that the joint surfaces 14 and 24 are joined to each other, and then the object 2 is tested. A typical cleaning process for pretreating glass for bonding is an SC1 cleaning process in which dilute hydrogen peroxide and a base (usually ammonium hydroxide, but also a tetramethylammonium hydroxide solution such as JT Baker JTB-100 or Clean the glass in JTB-111). Cleaning the self-joining surface removes the particles and makes the surface energy known, i.e., the cleaning provides baseline surface energy. The cleaning method does not have to be SC1, other types of cleaning can be used, as the type of cleaning may only have minimal effect on the stanol groups on the surface. The results of the various tests are set forth in Table 1 below.

Strong but separable by simply cleaning a thin glass piece of 100mm ² × 100μm thickness and a glass carrier in the form of a single mean flat (SMF) wafer of 0.50mm or 0.63mm thickness The initial room temperature or van der Waals bonding and/or hydrogen bonding, the thin glass sheet and the glass carrier each comprise Eagle XG® display glass (alkali-free aluminum borosilicate glass, average surface roughness Ra is approximately 0.2 nm, available from Corning Incorporated, Corning, NY). In this example, the glass was cleaned in a 40 °C: 40:1:2 DI water:JTB-111:hydrogen peroxide bath for 10 minutes. A thin glass or glass carrier may or may not be annealed in nitrogen at 400 ° C for 10 minutes to remove residual water, as indicated by the label "400 ° C" in the "Car" row or "Thin Glass" row in Table 1 below. The sample was annealed in nitrogen at 400 ° C for 10 minutes. The FPD process compatibility test showed that the initial room temperature bonding of this SC1-SC1 was mechanically strong enough to pass vacuum, SRD and ultrasonic testing. However, heating at 400 ° C and above 400 ° C creates a permanent bond between the thin glass and the carrier, ie, it cannot be moved without damage to one or both of the thin glass sheets and the carrier. In addition to thin glass sheets. And even for the case of Example 1c, wherein the carrier and the thin glass each have an annealing step to reduce the surface hydroxyl concentration. Thus, the bonding surfaces 14 and 24 are pretreated by separate heating as described above, and then the carrier 10 and the sheet 12 are bonded to the FPD process in the absence of the surface modifying layer 30 (wherein the temperature will 400 ° C) is not suitable for controlled bonding.

Pretreating the joint surface by reducing the hydroxyl group and the surface modifying layer

The reduced hydroxyl groups (e.g., by heat treatment) and the surface modifying layer 30 can be used together to control the interaction between the bonding surfaces 14, 24. For example, the bonding energy of the bonding surfaces 14, 24 (the room temperature van der Waals bonding and/or hydrogen bonding due to the polarity/dispersion energy component, and the high temperature covalent bonding due to the covalent energy component) can be controlled. In order to provide varying bond strengths, it is difficult to perform room temperature bonding to ease of room temperature bonding and to separate the bonded surfaces after high temperature processing to prevent separation of the surface without damage after high temperature processing. In some applications, it may be necessary to have no or very weak joints (such as when the surface is in a "non-joined" region, as described in the sheet/carrier concept of US '727 and as described below. region). Others are provided, for example, for FPD processes and similar processes (where achievable 500 ° C or In the application of reusable carriers at 600 ° C and process temperatures up to 650 ° C, it is necessary to have sufficient van der Waals bonding and/or hydrogen bonding at room temperature in order to initially place the sheets and carriers together, while Prevent or limit high temperature covalent bonding. For other applications, it may be necessary to have sufficient room temperature bonding to initially place the sheet and carrier together, and also create strong covalent bonding at elevated temperatures (eg, when the surface is in the "joining area", such as the sheet of US '727 / "joining area" as described in the vehicle concept and as discussed below. While not wishing to be bound by theory, in some cases, a surface modifying layer can be used to control room temperature bonding, by initially placing the sheets and carriers together by room temperature bonding, thereby reducing the hydroxyl groups on the surface (for example, It can be used to control covalent bonding, especially by high temperature covalent bonding, by heating the surface, or by reacting a hydroxyl group with a surface modifying layer.

The material for the surface modifying layer 30 can provide bonding surfaces 14, 24 having a certain energy (e.g., as measured for a surface of <40 mJ/m ² and including polar and dispersed components), whereby the surface is only produced Weakly engaged. In one example, hexamethyldisilazane (HMDS) can be used to make this low energy surface by reacting with surface hydroxyl groups to leave a trimethylsilyl (TMS) capping surface. HMDS as a surface modifying layer can be used with surface heating to reduce the hydroxyl concentration, thereby controlling both room temperature and high temperature bonding. By selecting a joint surface suitable for each of the joint surfaces 14, 24, an article having a range of capabilities can be achieved. More specifically, in the case of providing a reusable carrier for LTPS processing, a suitable bond can be achieved between the thin glass sheet 20 and the glass carrier 10 to withstand (or pass) the vacuum SRD. Each of the 400 ° C (Parts a and C) and 600 ° C (Parts a and C) were tested.

In one example, after a SC1 cleaning of both the thin glass and the carrier by HMDS processing, a weak bonding surface is created that challenges the room temperature bonding with a van der Waals (and/or hydrogen bonding) force. Apply mechanical force to engage thin glass and load With. As shown in Example 2a of Table 2, the bond was weak enough to observe deflection of the carrier during vacuum testing and SRD processing, and bubbling was observed in the 400 ° C and 600 ° C thermal processes (possibly due to outgassing). And particle defects were observed after the ultrasonic treatment.

In another example, HMDS treatment of only one surface (the carrier in the cited example) produces a stronger room temperature adhesion that can withstand vacuum and SRD processing. However, thermal processes above 400 ° C and above 400 ° C permanently bond the thin glass to the carrier. This result is unexpected, as the maximum surface coverage of trimethylsulfonyl on cerium oxide has been calculated by Sindorf and Maciel in J. Phys. Chem. 1982, 86, 5208-5219 to be 2.8/nm ² and by Suratlama Et al., 2.7/nm ² as measured in Journal of Non-Crystalline Solids 316 (2003) 349-363, has a hydroxyl group concentration of 4.6-4.9/nm ² relative to fully hydroxylated ceria. That is, although the trimethyldecyl group does bond with some surface hydroxyl groups, there will still be some unbonded hydroxyl groups. It will therefore be expected that if sufficient time and temperature are imparted, condensation of the surface stanol groups will permanently bond the thin glass to the carrier.

The altered surface energy can be produced by heating the surface of the glass prior to exposure of the HMDS to reduce the surface hydroxyl concentration, thereby increasing the polar component of the surface energy. This reduces the driving force for the formation of covalent Si-O-Si bonds at elevated temperatures and produces stronger room temperature bonds, such as van der Waals (and/or hydrogen) bonding. Figure 4 shows the surface energy of the Eagle XG® display glass carrier after annealing and after HMDS processing. Increasing the annealing temperature followed by HMDS exposure can increase the total (polar and dispersed) surface energy (line 402) by increasing the polarity contribution (line 404) after HMDS exposure. It can also be seen that the dispersion contribution of heat treatment to total surface energy (line 406) is It remains largely unchanged. While not wishing to be bound by theory, increasing the polar component of surface energy and thus increasing total surface energy after HMDS treatment appears to be due to exposure of some of the glass surface area due to sub-monolayer TMS coverage of HMDS after HMDS treatment.

In Example 2b, the thin glass sheets were heated in vacuum at a temperature of 150 ° C for one hour, followed by bonding with a carrier that was not heat treated and had an HMDS coating. This heat treatment of thin glass sheets is not sufficient to prevent thin glass sheets and carriers from being Permanently joined at a temperature of 400 °C.

As shown in Examples 2c to 2e of Table 2, changing the annealing temperature of the glass surface followed by HMDS exposure changes the bonding energy of the glass surface to control the bonding between the glass carrier and the thin glass sheet.

In Example 2c, the carrier was annealed in vacuum at a temperature of 190 ° C for 1 hour, followed by HMDS exposure to obtain a surface modifying layer 30. Further, the thin glass piece was annealed in vacuum at 450 ° C for 1 hour, and then joined to the carrier. The resulting article was subjected to vacuum, SRD and 400 ° C tests (Parts a and c, but failed to pass Part b due to increased bubbling), but did not pass the 600 ° C test. Therefore, although the high-temperature bonding property is increased as compared with the example 2b, the increase is insufficient to manufacture An article (eg, LTPS treated) that is processed at a temperature of 600 ° C, wherein the carrier is reusable.

In Example 2d, the carrier was annealed in vacuum at a temperature of 340 ° C for 1 hour, followed by HMDS exposure to obtain a surface modifying layer 30. The thin glass sheets were again annealed in vacuum at 450 ° C for 1 hour and then joined to the carrier. The results were similar to those in Example 2c, in which the article was subjected to vacuum, SRD and 400 ° C tests (Parts a and C, but failed due to increased bubbling) Passed part b) but did not pass the 600 °C test.

As shown in Example 2e, both the thin glass and the carrier were annealed in vacuum at 450 ° C for 1 hour, followed by HMDS exposure of the carrier, followed by bonding of the carrier to the thin glass sheet, thereby improving the permanent bond. Temperature resistance. Annealing both surfaces at 450 ° C prevents permanent bonding after RTP annealing at 600 ° C for 10 minutes, ie, the sample is tested by 600 ° C treatment (Parts a and C, but due to increased bubbling And did not pass part b; similar results were obtained in the 400 °C test).

In Examples 2a through 2e above, the carrier and the wafer were each Eagle XG® glass, wherein the carrier was a 630 micron thick 150 mm diameter SMF wafer and the wafer was 100 mm ² , 100 microns thick. HMDS was coated by pulsed vapor deposition in a YES-5 HMDS oven (available from Yield Engineering Systems, San Jose, CA) and was one atomic layer thick (ie, about 0.2 nm to 1 nm), but The surface coverage can be less than a single layer, i.e., some surface hydroxyl groups are not covered by HMDS, as noted by Maciel and discussed above. Since the thickness of the surface modifying layer is small, there is almost no risk of outgassing, and outgassing may cause contamination in the manufacture of components. In addition, as indicated by the "SC1" mark in Table 2, each of the carrier and the sheet is cleaned using the SC1 process followed by heat treatment or any subsequent HMDS treatment.

Comparative Example 2a and Example 2b show that the bonding energy between the sheet and the carrier can be controlled by varying the number of surfaces, including the surface modifying layer. And the control engagement energy can be used to control the engagement force between the two engagement surfaces. Further, Comparative Examples 2b to 2e show that the bonding energy of the surface can be controlled by changing the parameters of the heat treatment performed by bonding the surface before coating the surface modifying material. Again, heat treatment can be used to reduce the number of surface hydroxyl groups and thus control the extent of covalent bonding, especially high temperature covalent bonding.

Other materials that can function in different ways to control the surface energy on the bonding surface can be used in the surface modifying layer 30 to control the room temperature and high temperature bonding forces between the two surfaces. For example, if one or both of the bonding surfaces are modified by a surface modifying layer to create a medium bonding force, a reusable carrier can also be created that covers or sterically hinders the substance (eg, hydroxyl groups) ) to prevent strong permanent covalent bonds between the carrier and the sheet at elevated temperatures. One way to create an adjustable surface energy and cover the surface hydroxyl groups to prevent the formation of covalent bonds is to deposit a plasma polymer film, such as a fluoropolymer film. Plasma polymerization deposits a thin polymer film from a gas source under atmospheric or reduced pressure and plasma excitation (DC or RF parallel plates, inductively coupled plasma (ICP) electron cyclotron resonance (ECR) downstream microwave or RF plasma). The source of the gas is, for example, a fluorocarbon source (including CF ₄ , CHF ₃ , C ₂ F ₆ , C ₃ F ₆ , C ₂ F ₂ , CH ₃ F, C ₄ F ₈ , chlorofluorocarbon or hydrochlorofluorocarbon). Hydrocarbons, such as alkanes (including methane, ethane, propane, butane), alkenes (including ethylene, propylene), alkynes (including acetylene), and aromatic hydrocarbons (including benzene, toluene); hydrogen; and other gases Source, such as SF ₆ . Plasma polymerization produces a highly crosslinked layer of material. Controlling reaction conditions and gas sources can be used to control film thickness, density, and chemistry to tailor functional groups for the desired application.

Figure 5 shows the total (line 502) surface energy of a plasma polymerized fluoropolymer (PPFP) film deposited from a CF ₄ -C ₄ F ₈ mixture using an Oxford ICP380 etching tool (obtained from Oxford Instruments, Oxfordshire UK). A polar component (line 504) and a dispersion component (line 506) are included. The films were deposited on Eagle XG® glass sheets and the spectral ellipsometry revealed that the films were 1 nm to 10 nm thick. As can be seen from Figure 5, the glass carrier treated with a plasma-polymerized fluoropolymer film containing less than 40% C ₄ F ₈ exhibits a surface energy of >40 mJ/m ² and is obtained at room temperature by Val joint or hydrogen bonding creates a controlled bond between the thin glass and the carrier. Convenient bonding was observed when the carrier and the thin glass were initially joined at room temperature. That is, when the sheet is placed on the carrier and the sheet is pressed together with the carrier at one point, the wavefront travels across the carrier, but at a lower rate than the SC1 treated surface without the surface modifying layer thereon. The observed speed. The controlled joint is sufficient to withstand all standard FPD processes, including vacuum, wet, ultrasonic, and thermal processes up to 600 ° C, ie, this controlled joint is in the absence of thin glass self-carrier movement or thin glass and carrier In the case of the layer, the test was performed by 600 ° C. By use of razor blade as described above and / or Kapton ^TM tape stripping to release the engagement. The process compatibility of two different PPFP films (deposited as described above) is shown in Table 3. The PPFP 1 of Example 3a was formed with C ₄ F ₈ /(C ₄ F ₈ +CF ₄ )=0, that is, formed with CF ₄ /H ₂ instead of C ₄ F ₈ , and the PPFP 2 of Example 3b was C. ₄ F ₈ /(C ₄ F ₈ +CF ₄ )=0.38 deposition. Both types of PPFP films were subjected to vacuum, SRD, 400 ° C and 600 ° C processing tests. However, delamination was observed after 20 minutes of ultrasonic cleaning of PPFP 2, indicating that the adhesion was insufficient to withstand such treatment. Nevertheless, the surface modification layer PPFP2 can be used for some applications because ultrasonic processing is not necessary.

In Examples 3a and 3b above, the carrier and the wafer were each Eagle XG® glass, wherein the carrier was a 630 micron thick 150 mm diameter SMF wafer and the wafer was 100 mm ² , 100 microns thick. Since the thickness of the surface modifying layer is small, there is almost no risk of outgassing, and outgassing may cause contamination in the manufacture of components. In addition, since the surface modification layer does not appear to be degraded, the risk of outgassing is even smaller. Further, as indicated in Table 3, each of the sheets was cleaned using an SC1 process, followed by heat treatment in a vacuum at 150 ° C for one hour.

Still other materials that can function differently to control surface energy can be used as surface modifying layers to control room temperature and high temperature bonding forces between the sheet and the carrier. For example, a bonding surface that produces controlled bonding can be fabricated by subjecting a glass carrier and/or a glass sheet to a decane treatment. The decane is selected to produce a suitable surface energy and to have sufficient thermal stability for the application. The carrier to be treated or the thin glass can be cleaned by a process such as O ₂ plasma or UV-ozone and SC1 or standard cleaning 2 (SC2, known in the art) cleaning to remove turethane and surface decane Alcohol-based organics and other impurities (such as metals). It is also possible to use a washing based on other chemical reactions, such as HF or H ₂ SO _{4 , to} wash the chemical reaction. The carrier or thin glass can be heated prior to decane coating (as discussed above in connection with the HMDS surface modifying layer) to control the surface hydroxyl concentration and/or can be heated after the decane coating to complete the decane condensation with the surface hydroxyl groups. The concentration of unreacted hydroxyl groups after decaneization can be made sufficiently low before bonding to prevent thin glass and the carrier from being Permanent joining occurs at a temperature of 400 ° C, i.e., to form a controlled joint. This method is described below.

Example 4a

The glass surface of the bonded surface treated with O ₂ plasma and SC1 was then treated with toluene containing 1% dodecyltriethoxysilane (DDTS) and annealed in vacuum at 150 ° C for 1 hour to complete. condensation. The DDTS treated surface exhibited a surface energy of 45 mJ/m ² . As shown in Table 4, a glass flake (already cleaned by SC1 and heated in vacuum at 400 ° C for one hour) was bonded to the carrier engaging surface having the DDTS surface modifying layer thereon. The article was subjected to wet and vacuum process testing, but was unable to withstand a thermal process above 400 °C without the formation of bubbles under the carrier due to thermal decomposition of the decane. It is expected that this thermal decomposition is directed to all linear alkoxy and chloroalkyl decanes R1 _x Si(OR2) _y (Cl) _z , where x=1 to 3 and y+z=4-x, but can produce good thermal stability Except for methyl, dimethyl and trimethyl decane (x = 1 to 3, R1 = CH ₃ ) of the coating.

Example 4b

Subsequently, the glass carrier having the surface treated with O ₂ plasma and SC1 was treated with toluene containing 1% 3,3,3-trifluoropropyltriethoxysilane (TFTS), and The condensation was completed by annealing in a vacuum at 150 ° C for 1 hour. The surface treated by TFTS exhibited a surface energy of 47 mJ/m ² . As shown in Table 4, a glass flake (already cleaned by SC1, followed by heating in vacuum at 400 ° C for one hour) was bonded to the carrier engaging surface having the TFTS surface modifying layer thereon. This article was subjected to vacuum, SRD and 400 °C process tests without permanent bonding of the glass flakes to the glass carrier. However, the 600 ° C test produced bubbles which were formed under the carrier due to thermal decomposition of the decane. This is not surprising, as the thermal stability of the propyl is limited. Although this sample did not pass the 600 ° C test due to bubbling, the materials and heat treatment of this example can be used in applications where bubbles and their adverse effects, such as reduced surface smoothness or increased ripple, can be tolerated.

Example 4c

The glass surface of the joint surface treated with O ₂ plasma and SC1 was then treated with toluene containing 1% phenyltriethoxysilane (PTS) and annealed in vacuum at 200 ° C for 1 hour to complete the condensation. The PTS treated surface exhibited a surface energy of 54 mJ/m ² . As shown in Table 4, a glass flake (already cleaned by SC1, followed by heating in vacuum at 400 ° C for one hour) was bonded to the carrier engaging surface having the PTS surface modifying layer. This article withstands vacuum, SRD and a hot process up to 600 ° C without permanent bonding of the glass flakes to the glass carrier.

Example 4d

Subsequently, the glass carrier having the surface treated with O ₂ plasma and SC1 was treated with toluene containing 1% diphenyldiethoxysilane (DPDS), and annealed in vacuum at 200 ° C for 1 hour to complete the condensation. . The DPDS treated surface exhibited a surface energy of 47 mJ/m ² . As shown in Table 4, a glass flake (already cleaned by SC1, followed by heating in vacuum at 400 ° C for one hour) was bonded to the carrier engaging surface having the DPDS surface modifying layer. This article withstands vacuum and SRD testing and a hot process up to 600 ° C without permanent bonding of the glass flakes to the glass carrier.

Example 4e

Subsequently, the glass carrier with the surface treated with O ₂ plasma and SC1 was treated with toluene containing 1% 4-pentafluorophenyltriethoxysilane (PFPTS) and annealed in vacuum at 200 ° C. The condensation was completed in 1 hour. The surface treated by PFPTS exhibited a surface energy of 57 mJ/m ² . As shown in Table 4, a glass flake (already cleaned by SC1, followed by heating in vacuum at 400 ° C for one hour) was bonded to the carrier engaging surface with the PFPTS surface modifying layer. This article withstands vacuum and SRD testing and a hot process up to 600 ° C without permanent bonding of the glass flakes to the glass carrier.

In Examples 4a through 4e above, the carrier and the wafer were each Eagle XG® glass, wherein the carrier was a 630 micron thick 150 mm diameter SMF wafer and the wafer was 100 mm ² , 100 microns thick. The decane layer is a self-assembled monolayer (SAM) and thus is less than about 2 nm thick. In the above examples, a SAM was produced using an organic decane having an aryl or alkyl non-polar tail group and a mono-, di- or triolate head group. These decanes react with stanols on the surface of the glass to directly attach the organic functional groups. A weaker interaction between the non-polar head groups organizes the organic layer. Since the thickness of the surface modifying layer is small, there is almost no risk of outgassing, and outgassing may cause contamination in the manufacture of components. In addition, since the surface modifying layers of Examples 4c, 4d, and 4e do not appear to degrade, the risk of outgassing is even smaller. Further, as indicated in Table 4, each glass flake was cleaned using the SC1 process, followed by heat treatment in vacuum at 400 ° C for one hour.

As can be seen from Comparative Examples 4a through 4e, the surface energy of the control joint surface is higher than 40 mJ/m ^{2 in} order to promote initial room temperature bonding, not only in the case of producing a controlled joint capable of withstanding FPD treatment, but also in the case where no damage occurs. Remove the sheet from the carrier. In particular, as can be seen from Examples 4a through 4e, the surface energy of each carrier is above 40 mJ/m ² , thereby facilitating initial room temperature bonding to allow the article to withstand vacuum and SRD processing. However, Examples 4a and 4b did not pass the 600 °C processing test. As noted above, for certain applications, the bond is subjected to high temperatures without the degradation being degraded enough to hold the sheet together with the carrier and insufficient to control the degree of covalent bonding that occurs at such elevated temperatures. Process (for example 400 ° C, 500 ° C or 600 ° C, up to 650 ° C, as long as it is suitable for the process of designing the article, so that the permanent joint between the sheet and the carrier is also very important. As shown by way of example in Table 4, an aromatic decane, especially phenyl decane, can be used to provide a controlled bond that will promote initial room temperature bonding and will withstand FPD processing and yet allow for damage without damage. In case the strip is removed from the carrier.

The above separations in Examples 4, 3 and 2 were carried out at room temperature without adding any other thermal or chemical energy to modify the joint interface between the sheets and the carrier. The only energy input is mechanical tension and/or peel force.

The above materials of Examples 3 and 4 can be applied to the carrier, the sheet or the carrier and sheet surfaces to be joined together.

Use of controlled joints

Reusable vehicle

One use of controlled bonding via a surface modifying layer (including heat treatment of materials and associated joint surfaces) to provide the desired temperature Reuse of the carrier in an article at 600 ° C (for example in LTPS processing). The surface modifying layers (including material and bonding surface heat treatment) as exemplified in Examples 2e, 3a, 3b, 4c, 4d, and 4e above can be used to provide reuse of the carrier under such temperature conditions. In particular, such surface modifying layers can be used to modify the surface energy of the overlap region between the bonded sheet and the bonded regions of the carrier, whereby the entire sheet and carrier can be separated after processing. The sheets may be separated together or may be separated in portions, such as when the component fabricated on the portion of the sheet is first removed and the remainder removed thereafter to clean the carrier for reuse. In the case where the entire sheet is removed from the carrier, the carrier can be reused as it is by placing only another sheet thereon. Alternatively, the carrier can be cleaned and pre-treated to carry the sheet by reforming the surface modifying layer. Because the surface modifying layer prevents the sheet from permanently bonding to the carrier, the surface modifying layer can be used for temperature 600 ° C process. Of course, although these surface modifying layers can be at temperature Bonding surface energy is controlled during processing at 600 °C, but such surface modifying layers can also be used to fabricate sheets that withstand lower temperature processing in combination with carriers and can be used in such lower temperature applications to control bonding. Further, in the case where the heat treatment of the article does not exceed 400 ° C, the surface modifying layer as exemplified in Examples 2c, 2d, 4b can also be used in the same manner.

Provide controlled joint area

A second use of controlled bonding via a surface modifying layer (including heat treatment of the material and associated bonding surfaces) is to provide a controlled joint area between the glass carrier and the glass sheet. More specifically, by means of the surface modifying layer, a controlled joint region can be formed in which sufficient separation force can separate the sheet portion from the carrier without the damage of the sheet or carrier due to the joint, but throughout the process Adequate bonding force is maintained to hold the sheet relative to the carrier. Referring to FIG. 6, the glass sheet 20 can be joined to the glass carrier 10 by the joint region 40. In the joint region 40, the carrier 10 and the sheet 20 are covalently joined to each other such that the carrier and the sheet serve as a unit. Additionally, there is a controlled joint region 50 having a perimeter 52 in which the carrier 10 is attached to the sheet 20, but even at elevated temperatures (eg, temperature After treatment at 600 ° C, it can also be separated from each other. Although ten controlled joint regions 50 are shown in Figure 6, any suitable number may be provided, including one. The surface modifying layer 30 (including material and bonding surface heat treatment) as exemplified in Examples 2a, 2e, 3a, 3b, 4c, 4d, and 4e above can be used to provide a controlled bonding region 50 between the carrier 10 and the sheet 20. In particular, such surface modifying layers can be formed in the perimeter 52 of the controlled bonding region 50 on the carrier 10 or sheet 20. Thus, when the article 2 is processed at a high temperature to form a covalent bond in the joint region 40 or during component processing, a controlled bond can be provided between the carrier 10 and the sheet 20 in the region bounded by the perimeter 52, Thereby the separation force can be separated (without catastrophic damage to the sheet or carrier) of the sheets and carriers in this area, while the sheets and carriers do not delaminate during processing, including ultrasonic processing. The controlled engagement provided by the surface modifying layer and any associated heat treatment in this application can thus improve the carrier concept in US '727. In particular, although the joint perimeter and non-joining center regions of the US '727 carrier have been shown to withstand FPD processing, including High temperature processing at about 600 ° C, but ultrasonic processes (such as wet cleaning and resist stripping) remain challenging. In particular, it can be seen that the pressure wave in the solution induces and sympathic vibration in the non-joining region of the thin glass (as described in US '727 non-joining) because there is little or no binding in the region. Adhesion of thin glass to the carrier. Standing waves can be formed in the thin glass, wherein the waves can cause vibration, and if the ultrasonic agitation has sufficient strength, the vibrations can cause the thin glass to break at the interface between the joined region and the non-joined region. This problem can be eliminated by minimizing the gap between the thin glass and the carrier and by providing sufficient adhesion or controlled engagement between the carrier 20 and the thin glass 10 in such regions 50. The surface modifying layer of the bonding surface (including the materials exemplified as in Examples 2a, 2e, 3a, 3b, 4c, 4d, and 4e and any associated heat treatment) controls the bonding energy to provide sufficient bonding between the sheet 20 and the carrier 10 to Avoid such unwanted vibrations in the controlled joint area.

Subsequently, during extraction of the desired portion 56 having the perimeter 57, portions of the sheet 20 within the perimeter 52 and the carrier 10 can be simply separated after processing and after separation of the sheets along the perimeter 57. The surface modifying layer can be used for temperature because the surface modifying layer controls the bonding to prevent the sheet from permanently bonding to the carrier. 600 ° C process. Of course, although these surface modifying layers can be at temperature Bonding surface energy is controlled during processing at 600 °C, but such surface modifying layers can also be used to fabricate sheets that withstand lower temperature processing in combination with carriers and can be used in such lower temperature applications. In addition, in the case where the heat treatment of the article does not exceed 400 ° C, the surface modifying layer as exemplified in Examples 2c, 2d, 4b can also be used to control the bonding surface in the same manner (in some cases, depending on other process requirements). can.

Provide joint area

A third use for controlled bonding via a surface modifying layer (including heat treatment of the material and any associated bonding surfaces) is to provide a joint region between the glass carrier and the glass sheet. Referring to FIG. 6, the glass sheet 20 can be joined to the glass carrier 10 by the joint region 40.

In one embodiment of the third use, in the joint region 40, the carrier 10 and the sheet 20 can be covalently joined to each other such that the carrier and the sheet serve as a unit. Additionally, there is a controlled joint region 50 having a perimeter 52 in which the carrier 10 and sheet 20 are joined to each other sufficiently to withstand handling, and even at elevated temperatures (eg, temperature The separation of the sheet and the carrier is still allowed after the treatment at 600 °C. Thus, the surface modifying layer 30 (including material and bonding surface heat treatment) as exemplified in Examples 1a, 1b, 1c, 2b, 2c, 2d, 4a, and 4b above can be used to provide a joint region between the carrier 10 and the sheet 20. 40. In particular, such surface modifying layers and heat treatment can be formed on the carrier 10 or the perimeter 52 of the controlled bonding region 50 on the sheet 20. Thus, when the article 2 is processed at a high temperature or the article 2 is processed at a high temperature to form a covalent bond, the carrier and the sheet 20 will be joined to each other within the joint region 40 outside the region bounded by the perimeter 52. Subsequently, during the extraction of the desired portion 56 having the perimeter 57, when the sheet 20 and the carrier 10 need to be diced, the articles can be separated along the line 5 because of such surface modifying layers and heat treated covalently bonded sheets 20 and carriers 10. Therefore, the sheet and the carrier act as a whole in this area. Because the surface modifying layer provides permanent covalent bonding of the sheet to the carrier, the surface modifying layer can be used for temperature 600 ° C process. In addition, the initial formation of the heat treatment or joint region 40 of the article will In the case of 400 ° C but less than 600 ° C, the surface modifying layer as exemplified by the material and the heat treatment in Example 4a can also be used in the same manner.

In a second embodiment of the third use, in the joint region 40, the carrier 10 and the sheet 20 can be joined to each other by controlled engagement via the various surface modifying layers described above. Additionally, there is a controlled joint region 50 having a perimeter 52 in which the carrier 10 and sheet 20 are joined to each other sufficiently to withstand handling, and even at elevated temperatures (eg, temperature The separation of the sheet and the carrier is still allowed after the treatment at 600 °C. Thus, if treatment is to be carried out at temperatures up to 600 ° C and there is no need to have permanent or covalent bonding in region 40, the surface modification as exemplified by Examples 2e, 3a, 3b, 4c, 4d and 4e above The layer 30 (including material and joint surface heat treatment) can be used to provide a joint region 40 between the carrier 10 and the sheet 20. In particular, such surface modifying layers and heat treatments can be formed outside of the perimeter 52 of the controlled bonding region 50 and can be formed on the carrier 10 or sheet 20. The controlled bonding region 50 may be formed with a surface modifying layer that is the same as or different from the surface modifying layer formed in the bonding region 40. Alternatively, if processing is to be carried out at temperatures up to only 400 ° C and there is no need to have permanent or covalent bonding in region 40, as by examples 2c, 2d, 2e, 3a, 3b, 4b, 4c, 4d above The surface modifying layer 30 (including material and bonding surface heat treatment) exemplified by 4e can be used to provide the bonding region 40 between the carrier 10 and the sheet 20.

As an alternative to controlled bonding in region 50, there may be non-joining regions in region 50, wherein the non-joining regions may be regions of increased surface roughness as described in US '727, or may be A surface modifying layer as exemplified in Example 2a is provided.

For the manufacture of electronic components

A fifth use of controlled joints as described herein is the manufacture of glass articles comprising glass articles having a carrier and a sheet joined to the carrier, which are in turn used in the manufacture of electronic components, such as TFTs, OLEDs (including organic light-emitting materials), PV elements, touch sensors, and displays. For example, a reusable carrier as described above can be used. Alternatively, for example, a glass material having a joint region and a controlled joint region as described above may be used. Pieces.

In any event, an electronic component processing apparatus such as that currently designed for thicker sheets can be used to process a glass article to position an electronic component component or an electronic component component on the sheet of the article. The electronic component assembly should be placed in a portion of the wafer that engages the carrier via the controlled bonding described above, whereby the wafer can be separated from the carrier even after processing to the temperature necessary to manufacture the electronic component. Component processing can be included, for example 400 ° C, 500 ° C, Treat at 600 ° C or up to 650 ° C. As noted above, a suitable surface modifying layer can be selected to allow the sheet to be removed from the carrier even after processing at such temperatures, without at least damaging the sheet and preferably not damaging both the sheet and the carrier. To this end, many electronic component assemblies can be placed in many steps until the electronic components are completed or in an appropriate intermediate stage. The article can be assembled prior to processing of the electronic component or can be assembled as part of an electronic component manufacturing process.

Component processing can include maintaining the integrity of the article throughout the component processing, or can include cutting the object at one or more points in the process. For example, component processing can include forming an electronic component assembly on an object, then cutting the article into two or more portions, and then further processing the portions, ie, another component of the electronic component The electronic component assembly disposed on the sheet or on the sheet and disposed by the previous step. The cutting step can be performed such that portions of the article include portions of the sheet that remain engaged with the carrier, or such that only a subset of the portions of the cut include such a configuration. Within any of the cut portions, the entire sheet area in the portion can remain engaged with the entire carrier region in the portion.

After the component is processed or reaches the intermediate stage, it can be moved up from the carrier. In addition to the device and the portion of the sheet on which the device is placed. The sheet may be removed in its entirety, or a portion thereof may be separated from the remainder and from the portion from which the carrier is removed. The removal can be performed from the entire article or from one or more portions of the article.

Breathing

Polymeric adhesives used in typical wafer bonding applications are typically from 10 microns to 100 microns thick and lose about 5% of their mass at or near their temperature extremes. For such materials evolved from thick polymer films, it is easy to quantify the amount of mass loss or outgassing by mass spectrometry. On the other hand, it is more challenging to measure the outgassing of a thin surface treatment of about 10 nm thick or thinner, such as the above-described plasma polymer or self-assembled monolayer surface modifying layer and a thin layer of thermally depolymerized polyoxygenated oil. For this material, the mass spectrum is not sensitive enough. However, there are many other ways to measure outgassing.

The first way to measure a small amount of outgassing is based on surface energy measurements and will be described with reference to Figure 7. For this test, a device as shown in Figure 7 can be used. The first substrate or carrier 900 having the surface modifying layer to be tested thereon provides a surface 902, i.e., a surface modifying layer corresponding to the surface modifying layer 30 to be tested in composition and thickness. The second substrate or cover 910 is placed such that its surface 912 is in close proximity to the surface 902 of the carrier 900 but not in contact with each other. Surface 912 is the uncoated surface, that is, the surface of the bare material from which the cover is made. Spacer 920 is placed at a different point between carrier 900 and cover 910 to maintain the carrier and cover in spaced relationship relative to one another. Spacer 920 should be thick enough to separate cover 910 from carrier 900 to allow material to move from one to the other, but thin enough to surface 902 and 912 during testing. The amount of contamination due to the atmosphere of the chamber is minimized. Carrier 900, spacer 920, and cover 910 together form test article 901.

Prior to assembly of the test article 901, the surface energy of the bare surface 912 is measured, and the surface energy of the surface 902 (i.e., the surface of the surface of the carrier 900 on which the surface modifying layer is disposed) is also measured. The surface energy (polarity) as shown in Fig. 8 was measured by fitting the theoretical model developed by S. Wu (1971) to the three contact angles of three test liquids (water, diiodomethane and hexadecane). Component and dispersion component). (Reference: S. Wu, J. Polym. Sci. C, 34, 19, 1971).

After assembly, the test article 901 is placed in the heating chamber 930 and heated by a time-temperature cycle. And heated in flowing N ₂ gas (i.e., a flow rate of 2 standard liters / minute in the direction of arrow 940) at atmospheric pressure.

During the heating cycle, surface energy changes of surface 902 demonstrate changes in surface 902 (including, for example, changes in surface modifying layers due to evaporation, pyrolysis, decomposition, polymerization, reaction with the vehicle, and dehumidification). The surface energy change of surface 902 does not necessarily mean that the surface modifying layer undergoes outgassing, but does indicate that the material is generally unstable at this temperature because its characteristics change, for example, due to the above mechanism. Thus, the smaller the surface energy of the surface 902 is, the more stable the surface modifying layer is. On the other hand, since surface 912 is in close proximity to surface 902, any material that is outgassed by surface 902 will collect on surface 912 and will alter the surface energy of surface 912. Thus, the surface energy change of surface 912 represents the outgassing of the surface modifying layer present on surface 902.

Thus, a outgassing test uses surface energy variations of the cover surface 912. In particular, if the surface of surface 912 can change At 10 mJ/m ² , there is outgassing. The change in surface energy of this magnitude is consistent with contamination that can cause film adhesion loss or degradation of material properties and component performance. Surface energy change 5mJ/m ^{2 is} close to the repeatability of surface energy measurement and the unevenness of surface energy. This small change is consistent with minimal outgassing.

During the test that produced the results in Figure 8, the carrier 900, cover 910, and spacer 920 were made of Eagle XG glass, which is an alkali-free aluminum boron boring obtained from Corning Incorporated (Corning, NY). Acidate display grade glass, but this need not be the case. Carrier 900 and cover 910 are 150 mm in diameter and 0.63 mm thick. In general, carrier 910 and cover 920 will each be made of the same material as carrier 10 and sheet 20 that require a gassing test. During this test, the spacers were 0.63 mm thick, 2 mm wide, and 8 cm long, creating a gap of 0.63 mm between surfaces 902 and 912. During this test, chamber 930 was incorporated into the MPT-RTP600s rapid thermal processing equipment, which was cycled from room temperature to the test limit temperature at a rate of 9.2 ° C/min, and maintained at the test limit temperature as "annealing time" in the graph. The different times are shown and then cooled to 200 ° C at the furnace rate. After the oven has cooled to 200 ° C, the test article is removed and the surface energy of each surface 902 and 912 is again measured after the test article has cooled to room temperature. Thus, for example, for the No. 1 material (line 1003), the change in the surface energy of the cover tested at the limit temperature of 450 ° C was used, and the data was collected as follows. The data points at 0 minutes show a surface energy of 75 mJ/m ² (mJ/m 2 ) and are the surface energy of bare glass, that is, have not undergone a time-temperature cycle. The data point at one minute indicates the surface energy measured after the time-temperature cycle as follows: the object 901 (using the No. 1 material as the surface modifying layer on the carrier 900 to provide the surface 902) is placed. In a heating chamber 930 at room temperature and atmospheric pressure; the chamber is heated to a test limit temperature of 450 ° C at a rate of 9.2 ° C/min with N ₂ gas flowing at two standard liters per minute, and The test limit temperature was maintained at 450 ° C for 1 minute; then the chamber was allowed to cool to 300 ° C at a rate of 1 ° C/min, and then the article 901 was removed from the chamber 930; the article was then allowed to cool to room temperature (none N ₂ flow atmosphere); the surface energy of surface 912 is then measured and plotted on line 1003 as a point of 1 minute. The remaining data points of material No. 1 (lines 1003, 1004) and material No. 2 (lines 1203, 1204), material No. 3 (lines 1303, 1304), material No. 4 (line 1403) are then determined in a similar manner. 1404), material No. 5 (line 1503, 1504) and material No. 6 (line 1603 and 1604), where the number of minutes of annealing corresponds to the test limit temperature (450 ° C or 600 ° C, as appropriate) Hold time. For the respective surface modifying layer materials (material Nos. 1 to 6), lines 1001, 1002, 1201, 1202, 1301, 1302, 1401, 1402, 1501, and 1502 representing the surface energy of the surface 902 are determined in a similar manner. The data points of 1601 and 1602, but the surface energy of surface 902 is measured after each time-temperature cycle.

The above assembly process and time-temperature cycle were performed for six different materials as described below, and the results are shown in Figure 8. Among the six materials, the materials No. 1 to No. 4 correspond to the above-mentioned surface modifying layer material. Materials No. 5 and No. 6 are comparative examples.

The No. 1 material is a CHF ₃ -CF ₄ plasma polymerization type fluoropolymer. This material is consistent with the surface modifying layer of Example 3b above. As shown in Figure 8, lines 1001 and 1002 show that the surface energy of the carrier does not change significantly. Thus, this material is extremely stable at temperatures between 450 ° C and 600 ° C. In addition, as shown by lines 1003 and 1004, the surface energy of the cover does not change significantly, that is, the change 5mJ/m ² . Therefore, there is no outgassing associated with this material from 450 ° C to 600 ° C.

The No. 2 material was phenyl decane, which was a self-assembled monolayer (SAM) deposited from a 1% toluene solution of phenyltriethoxydecane and cured in a vacuum oven at 190 ° C for 30 minutes. This material is consistent with the surface modifying layer of Example 4c above. As shown in Figure 8, lines 1201 and 1202 indicate some variation in surface energy on the carrier. As indicated above, this indicates some variation in the surface modifying layer, and in comparison, the No. 2 material is somewhat less stable than the No. 1 material. However, as shown by lines 1203 and 1204, the surface energy of the vehicle changes. 5mJ/m ² , showing that the change of the surface modification layer did not cause outgassing.

The No. 3 material was pentafluorophenyl decane, which was a SAM deposited from a 1% toluene solution of pentafluorophenyltriethoxydecane and cured in a vacuum oven at 190 ° C for 30 minutes. This material is consistent with the surface modifying layer of Example 4e above. As shown in Figure 8, lines 1301 and 1302 indicate some variation in surface energy on the carrier. As indicated above, this indicates some variation in the surface modifying layer, and in comparison, the No. 3 material is somewhat less stable than the No. 1 material. However, as shown by lines 1303 and 1304, the surface energy of the vehicle changes. 5mJ/m ² , showing that the change of the surface modification layer did not cause outgassing.

Material No. 4 was hexamethyldioxane (HMDS) self-vapor deposited at 140 ° C in a YES HMDS oven. This material is consistent with the surface modifying layer of Example 2b of Table 2 above. As shown in Figure 8, lines 1401 and 1402 indicate some variation in surface energy on the carrier. As indicated above, this indicates some variation in the surface modification layer, and in comparison, the No. 4 material is somewhat less stable than the No. 1 material. In addition, the surface energy of the material of the No. 4 material is changed more than any of the No. 2 and No. 3 materials, and the comparison indicates that the No. 4 material is not as stable as the No. 2 and No. 3 materials. . However, as shown by lines 1403 and 1404, the surface energy of the carrier changes. 5 mJ/m ² , showing that the change of the surface modification layer did not cause outgassing which would affect the surface energy of the cover. However, this is consistent with the venting method of HMDS. That is, HMDS release does not affect the surface energy of the cover and may not affect some electronic manufacturing equipment and/or treated ammonia and water. On the other hand, there may be other problems when capturing the outgassing product between the sheet and the carrier, as described below in connection with the second outgassing test.

No. 5 material was glycidoxypropyl decane, which was a SAM deposited from a 1% toluene solution of glycidoxypropyl triethoxy decane and cured in a vacuum oven at 190 ° C for 30 minutes. This material is a comparative example material. Although the surface energy of the carrier as shown by lines 1501 and 1502 is relatively minimal, the surface energy of the cover as shown by lines 1503 and 1504 varies significantly. That is, although material No. 5 is relatively stable on the surface of the carrier, it does release a large amount of material on the surface of the cover, thereby changing the surface energy of the cover. 10mJ/m ² . Although the surface energy at 100 ° C at the end of 10 minutes was within 10 mJ/m ² , the change during this time did exceed 10 mJ/m ² . See, for example, the data points at 1 minute and 5 minutes. While not wishing to be bound by theory, a slight increase in surface energy from 5 minutes to 10 minutes may be due in part to decomposition of the gassing material and detachment from the surface of the cover.

Material No. 6 was DC704, which was placed on a vehicle by dispersing 5 ml of Dow Corning 704 diffusion pump oil tetramethyltetraphenyltrioxane (available from Dow Corning) on the vehicle. A polyfluorene oxide coating pretreated in air at a 500 ° C hot plate for 8 minutes. The visible end of smoke indicates that sample pretreatment is complete. After the sample was pretreated in the above manner, the above gas release test was performed. This material is a comparative example material. As shown in Figure 8, lines 1601 and 1602 indicate some variation in surface energy on the carrier. As indicated above, this indicates some variation in the surface modifying layer, and in comparison, material No. 6 is somewhat less stable than material No. 1. In addition, as indicated by lines 1603 and 1604, the surface energy of the vehicle varies. 10 mJ/m ² , thus showing significant outgassing. More specifically, at a test limit temperature of 450 ° C, the 10-minute data point showed a surface energy reduction of about 15 mJ/m ² , and at 1 minute and 5 minutes, the surface energy was reduced even more. Similarly, at the 10 minute data point, the surface energy change during the cycle at 600 ° C test limit temperature (ie, the surface energy of the cover is reduced) is about 25 mJ/m ² , which is somewhat larger at 5 minutes. And 1 minute is a little smaller. In summary, however, this material showed a large amount of outgassing throughout the test range.

Obviously, for materials No. 1 to No. 4, the surface energy in the entire time-temperature cycle indicates that the surface energy of the surface of the cover still conforms to the surface energy of the bare glass, that is, the surface of the carrier is not collected. material. In the case of material No. 4, as shown in connection with Table 2, the manner in which the surface of the carrier and the sheet are pretreated is such that the article (the sheet and the carrier are joined together via the surface modifying layer) can withstand the FPD treatment. Great difference. Thus, although examples of material No. 4 shown in FIG. 8 may not be outgassed, this material may withstand or may not withstand the 400 ° C or 600 ° C test, as shown in the discussion in conjunction with Table 2.

A second way of measuring a small amount of outgas is based on an assembled article (i.e., an article with which the sheet is bonded to the carrier via the surface modifying layer) and uses a percentage change in the bubble region to determine outgassing. That is, during heating of the article, the bubbles formed between the carrier and the sheet indicate that the surface modifying layer is out of gas. As described above in connection with the first outgassing test, it is difficult to measure the outgassing of the extremely thin surface modifying layer. In this second test, outgassing under the sheet can be limited by strong adhesion between the sheet and the carrier. despite this, A 10 nm thick layer (e.g., plasma polymerized material, SAM, and pyrolytic polyoxyxene surface treatment) can still generate bubbles during heat treatment despite its small absolute mass loss. And creating bubbles between the sheet and the carrier can cause problems with patterning, photolithographic processing, and/or alignment on the sheet during component processing. In addition, bubbling at the boundary of the joint between the sheet and the carrier can cause a process flow of the process to contaminate the downstream process. Bubble area percentage change 5 is significant, indicating outgassing and undesirable. On the other hand, the percentage change in the bubble area 1 is not significant and indicates no outgassing.

The average bubble area of the bonded thin glass manually joined in the Class 1000 clean room is 1%. The percentage of bubbles in the bond carrier varies with the cleanliness of the carrier, the thin glass sheet, and the surface pretreatment. Since these initial defects act as nucleation sites for bubble growth after heat treatment, any bubble region change of less than 1% after heat treatment is within the sample pretreatment variability. For this test, a first scanned image of the area of the bond sheet and the carrier was created immediately after bonding using a commercially available desktop scanner (Epson Expression 10000 XL Photo) with a transparency unit. These parts were scanned using 508 dpi (50 micron/pixel) and 24-bit RGB using standard Epson software. The image processing software first preprocesses the image by stitching the images of different portions of the sample into a single image and removing the scanner artifacts (by using a calibration reference scan without a sample in the scanner) as needed. The junction area is then analyzed using standard image processing techniques such as thresholding, hole filling, erosion/expansion, and blob analysis. A newer Epson Expression 11000XL Photo can also be used in a similar manner. In the transfer mode, the bubbles in the joint area are visible in the scanned image and the value of the bubble area can be determined. Subsequently, the bubble area is compared to the total joint area (i.e., the total overlap area between the sheet and the carrier) to calculate the percentage of the area of the bubble in the joint area relative to the total joint area. The samples were then heat treated in the MPT-RTP 600s rapid heat treatment system at a test limit temperature of 300 ° C, 450 ° C and 600 ° C for up to 10 minutes under a N ₂ atmosphere. Specifically, the time-temperature cycle performed includes: inserting the article into a heating chamber at room temperature and atmospheric pressure; then heating the chamber to a test limit temperature at a rate of 9 ° C/min; The test was held for 10 minutes at the test limit temperature; the chamber was then cooled to 200 ° C at the furnace rate; the article was removed from the chamber and allowed to cool to room temperature; then the article was scanned a second time with an optical scanner. The percentage of bubble regions of the second scan is then calculated as above and compared to the percentage of bubble regions of the first scan to determine the percent change in bubble region (Δ bubble region %). As mentioned above, bubble area changes 5% is significant and indicates outgassing. Due to the variability of the percentage of the original bubble area, the percentage change of the bubble area is selected as the measurement criterion. That is, in the first scan, the bubble area of most of the surface modifying layer is about 2% due to the handling and cleanliness after the sheet and the carrier are pretreated and before the sheet is bonded to the carrier. However, it may change due to materials. In this second outgassing test method, the same materials No. 1 to No. 6 as those described for the first outgassing test method were used again. Among these materials, materials No. 1 to No. 4 exhibited about 2% of the bubble area in the first scan, while No. 5 and No. 6 materials showed a significantly larger bubble area in the first scan, that is, about 4%.

The results of the second outgassing test will be described with reference to Figs. 9 and 10. The results of the outgassing test for the materials No. 1 to No. 3 are shown in Fig. 9, and the results of the outgassing test for the materials No. 4 to No. 6 are shown in Fig. 10.

The results of the No. 1 material are illustrated in Figure 9 as square data points. As can be seen from the figure, for the test limit temperatures of 300 ° C, 450 ° C, and 600 ° C, the percentage of bubble regions changes to near zero. Therefore, material No. 1 showed no outgassing at these temperatures.

The results of the No. 2 material are illustrated in Figure 9 as diamond-shaped data points. As can be seen from this figure, for the test limit temperatures of 450 ° C and 600 ° C, the percentage change in bubble area is less than one. Therefore, material No. 2 showed no outgassing at these temperatures.

The result of the No. 3 material is illustrated in Figure 9 as a triangular data point. As can be seen from the figure, similar to the No. 1 material, the percentage of the bubble region changes to near zero for the test limit temperatures of 300 ° C, 450 ° C, and 600 ° C. Therefore, material No. 1 showed no outgassing at these temperatures.

The result of material No. 4 is illustrated in Figure 10 as a circular data point. As can be seen from the figure, for the test limit temperature of 300 ° C, the percentage of bubble area changes to near zero, but at 450 ° C and 600 ° C test limit temperature for some samples is close to 1%, and at 450 ° C and 600 ° C At the test limit temperature, about 5% of the other samples of the same material. The results of material No. 4 are very inconsistent and depend on the manner in which the sheets and the surface of the carrier are pretreated for bonding using HMDS materials. The manner in which the sample performance depends on the sample pretreatment method is consistent with the examples and related discussion of this material as set forth in Table 2 above. It should be noted that According to the separation test described above, for this material, the sample with a percentage change in the bubble area at a test limit temperature of 450 ° C and 600 ° C was close to 1%, and the separation sheet and the carrier were not allowed. That is, strong adhesion between the sheet and the carrier can limit bubble generation. On the other hand, a sample with a bubble cell percentage change of approximately 5% does allow separation of the wafer from the carrier. Thus, the non-gassing sample has the following undesirable results: increased adhesion after temperature treatment, thereby adhering the carrier to the sheet (preventing removal of the sheet from the carrier), allowing removal of the sheet and carrier The sample has an undesirable outgassing result.

The result of material No. 5 is illustrated in Figure 10 as a triangular data point. As can be seen from this figure, for a test limit temperature of 300 ° C, the percentage change in bubble area is about 15%, and far exceeds the percentage change of bubble area at a higher test limit temperature of 450 ° C and 600 ° C. Therefore, material No. 5 showed significant outgassing at these temperatures.

The results of the No. 6 material are illustrated in Figure 10 as square data points. As can be seen from this figure, for a test limit temperature of 300 ° C, the percentage of bubble regions varies by more than 2.5%, and exceeds 5% for test limit temperatures of 450 ° C and 600 ° C. Therefore, material No. 6 showed significant outgassing at the test limit temperatures of 450 ° C and 600 ° C.

in conclusion

It should be emphasized that the above-described embodiments of the present invention, and in particular, the preferred embodiments are merely illustrative of the embodiments of the invention, and are merely illustrative of the various concepts of the invention. Many variations and modifications of the above-described embodiments of the invention are possible without departing from the spirit and scope of the invention. All such modifications and variations are intended to be included herein in the present disclosure and the present invention. Within the scope and protection of the following patent application.

For example, while the surface modifying layer 30 of many embodiments is shown and discussed as being formed on the carrier 10, the surface modifying layer may alternatively or additionally be formed on the sheet 20. That is, the materials as set forth in Examples 4 and 3 can be applied to the side of the carrier 10, sheet 20 or carrier 10 and sheet 20 that will be joined together.

In addition, although some surface modifying layers 30 are described as controlling the bonding strength to allow removal of the sheet 20 from the carrier 10 even after processing the article 2 at a temperature of 400 ° C or 600 ° C, it is possible to be lower than the article The article 2 is processed at the temperature of the temperature of the particular test and is still capable of removing the sheet 20 from the carrier 10 without damaging the sheet 20 or the carrier 10.

Moreover, while the controlled bonding concept has been described herein as being used for carriers and sheets, in some cases these concepts are suitable for controlling the bonding between thicker glass sheets, ceramic sheets or glass ceramic sheets, wherein It may be desirable to detach the sheets (or portions of the sheets) from one another.

Moreover, while the controlled bonding concept has been described herein as being applicable to glass carriers and glass sheets, the carrier can be made of other materials such as ceramics, glass ceramics, or metals. Likewise, the sheet that can be controlled in engagement with the carrier can be made of other materials such as ceramic or glass ceramic.

The various concepts described above in accordance with the present application can be combined with each other in any and all different combinations. For example, the various concepts can be combined according to the following aspects.

According to a first aspect, a method of fabricating an electronic component is provided, the method comprising: Obtaining a carrier having a carrier engaging surface; obtaining a sheet having a sheet engaging surface; placing a surface modification on the carrier engaging surface and one of the sheet engaging surfaces a bonding layer that engages the sheet engaging surface with the sheet modifying surface between the carrier engaging surface and the sheet engaging surface to form an article such that the sheet is joined The surface energy of the carrier has the following characteristics: by circulating from room temperature to 600 ° C at a rate of 9.2 ° C / min, maintaining at a temperature of 600 ° C for 10 minutes, and then cooling to 300 ° C at 1 ° C / min. Heating the chamber to subject the article to temperature cycling, then removing the article from the chamber and allowing the article to cool to room temperature if the carrier and one of the sheets are held while the other Subject to gravity, the carrier and the sheet are not separated from each other, the surface modifying layer does not undergo outgassing during the temperature cycle, and can be broken into two pieces without causing the carrier and the thinner of the sheet to be broken. Or separating the sheet and the carrier in two or more cases; An electronic component element disposed on the sheet.

According to a second aspect, a method of fabricating an electronic component is provided, the method comprising the steps of: obtaining a glass article comprising: a carrier having a carrier engaging surface; a sheet of material The material has a sheet joining surface; a surface modifying layer disposed on one of the carrier engaging surface and the sheet engaging surface; the carrier engaging surface and the sheet engaging surface borrowing Engaged by the carrier The surface is bonded to the surface modifying layer between the sheet engaging surfaces, wherein bonding the sheet to the surface of the carrier can be characterized by cycling from room temperature to 600 at a rate of 9.2 ° C/min. °C, heating at a temperature of 600 ° C for 10 minutes, followed by cooling at 1 ° C / min to 300 ° C to subject the article to temperature cycling, then removing the article from the chamber and allowing the article to cool After the room temperature, if one of the carrier and the sheet is held and the other is subjected to gravity, the carrier and the sheet are not separated from each other, and the surface modifying layer does not release during the temperature cycle. Gas, and the sheet and the carrier can be separated without breaking the carrier and the thinner one of the sheets into two or more pieces; an electronic component assembly is placed on the sheet .

According to a third aspect, there is provided a method of the first aspect or the second aspect, wherein the electronic component assembly comprises an organic luminescent material.

According to a fourth aspect, a method of any one of the first aspect to the third aspect, wherein the processing the electronic component is included The treatment was carried out at a temperature of 400 °C.

According to a fifth aspect, a method of any one of the first aspect to the third aspect, wherein the processing the electronic component is included The treatment was carried out at a temperature of 600 °C.

According to a sixth aspect, there is provided a method of any one of the first aspect to the fifth aspect, the method further comprising the step of cutting the carrier and the sheet into two separate portions.

According to a seventh aspect, the method of the sixth aspect, wherein the at least one of the two separate portions comprises a sheet portion that is held in engagement with the carrier portion Minute

According to an eighth aspect, there is provided a method of the sixth aspect or the seventh aspect, the method further comprising the step of further processing at least one of the independent portions having additional electronic component components.

According to a ninth aspect, the method of any one of the first aspect to the eighth aspect is provided, the method further comprising the step of removing at least a portion of the sheet from the carrier, wherein the sheet is At least a portion includes the electronic component assembly on the at least a portion.

According to a tenth aspect, the method of any one of the first aspect to the ninth aspect, wherein the carrier comprises glass.

According to an eleventh aspect, the method of any one of the first aspect to the tenth aspect, wherein the carrier having no surface modifying layer has an average surface roughness of Ra 2nm.

According to a twelfth aspect, the method of any one of the first aspect to the eleventh aspect, wherein the carrier has a thickness of from 200 micrometers to 3 mm.

According to a thirteenth aspect, the method of any one of the first aspect to the twelfth aspect, wherein the sheet comprises glass.

According to a fourteenth aspect, the method of any one of the first aspect to the thirteenth aspect, wherein the sheet having no surface modifying layer has an average surface roughness of Ra 2nm.

According to a fifteenth aspect, the method of any one of the first aspect to the fourteenth aspect, wherein the thickness of the sheet is 300 microns.

According to a sixteenth aspect, the method of any one of the first aspect to the 15th aspect, wherein the surface modifying layer has a thickness of from 0.1 nm to 100 nm.

According to a seventeenth aspect, the method of any one of the first aspect to the 15th aspect, wherein the surface modifying layer has a thickness of from 0.1 nm to 10 nm.

According to an eighteenth aspect, the method of any one of the first aspect to the 15th aspect, wherein the surface modifying layer has a thickness of 0.1 nm to 2 nm.

According to a nineteenth aspect, the method of any one of the first aspect to the 18th aspect, wherein the carrier and the sheet each have a size of 100 mm × 100 mm or more.

According to a twentieth aspect, the method of any one of the first aspect to the 19th aspect, wherein the surface modifying layer comprises one of: a) a plasma polymerized fluoropolymer; and b) Aromatic decane.

According to a twenty-first aspect, the method of the twentieth aspect, wherein, when the surface modifying layer comprises a plasma polymerizable fluoropolymer, the surface modifying layer is one of the following: a plasma polymerization type polymerization Tetrafluoroethylene; A plasma-polymerized fluoropolymer surface modifying layer of 40% C ₄ F ₈ CF ₄ -C ₄ F ₈ mixture deposited.

According to a twenty-second aspect, the method of the twentieth aspect, wherein when the surface modifying layer comprises an aromatic decane, the surface modifying layer is one of: phenyl triethoxy decane; diphenyl Diethoxy decane; and 4-pentafluorophenyl triethoxy decane.

According to a twenty-third aspect, the method of the twentieth aspect, wherein the surface modifying layer contains a chlorophenyl fluorenyl group or a fluorophenyl fluorenyl group, when the surface modifying layer contains an aromatic decane.

14‧‧‧ joint surface

26‧‧‧The periphery of the sheet

28‧‧‧Sheet thickness

30‧‧‧ Surface modification layer

38‧‧‧The thickness of the surface modification layer

Claims (12)

A method of manufacturing an electronic component, the method comprising the steps of: obtaining a carrier having a carrier engaging surface; obtaining a sheet having a sheet engaging surface; and engaging the surface of the carrier and Disposing a surface modifying layer on one of the sheet engaging surfaces; causing the carrier engaging surface and the sheet engaging surface to be between the carrier engaging surface and the sheet engaging surface The case is joined to form an article such that joining the sheet to the surface of the carrier can be characterized by cycling from room temperature to 600 ° C at a rate of 9.2 ° C/min, at a temperature of 600 ° C. Heating the article for 10 minutes, followed by cooling to 300 ° C at 1 ° C/min to subject the article to temperature cycling, then removing the article from the chamber and allowing the article to cool to room temperature, if the load If the one of the sheets is held by the other and the other is subjected to gravity, the carrier and the sheet are not separated from each other, the surface modifying layer does not undergo outgassing during the temperature cycle, and the Vehicle and the thinner of the sheet Separating the carrier sheet and the case where two or more fragmented into two sheets; and an electronic component disposed on the sheet assembly. A method of manufacturing an electronic component, the method comprising the steps of: obtaining a glass article, the glass article comprising: a carrier having a carrier engaging surface; a sheet having a sheet engaging surface a surface modifying layer disposed on the bonding surface of the carrier And one of the sheet engaging surfaces; the carrier engaging surface and the sheet engaging surface are joined by the surface modifying layer between the carrier engaging surface and the sheet engaging surface, wherein the joining The surface of the sheet and the carrier can be characterized by being circulated from room temperature to 600 ° C at a rate of 9.2 ° C/min, held at a temperature of 600 ° C for 10 minutes, and then cooled at 1 ° C/min. Heating the chamber to 300 ° C to subject the article to temperature cycling, then removing the article from the chamber and allowing the article to cool to room temperature if one of the carrier and the sheet is held While the other is subjected to gravity, the carrier and the sheet are not separated from each other, the surface modifying layer does not generate outgas during the temperature cycle, and may not be thinner in the carrier and the sheet. The sheet and the carrier are separated in the case of breaking into two or more sheets; an electronic component assembly is placed on the sheet. The method of claim 1 or claim 2, wherein the electronic component component comprises an organic light emitting material. The method of claim 1 or 2, wherein the step of processing the electronic component comprises the steps of: The treatment was carried out at a temperature of 400 °C. The method of claim 1 or 2, the method further comprising the step of cutting the carrier and the sheet into two separate portions. The method of claim 5, wherein at least one of the independent portions A portion of the sheet that is held in engagement with a carrier portion. The method of claim 6, the method further comprising the step of processing the at least one of the independent portions, the independent portions having an additional electronic component assembly. The method of claim 1 or 2, the method further comprising the step of removing at least a portion of the sheet from the carrier, wherein the at least a portion of the sheet comprises the electronic component assembly on the at least a portion. The method of claim 1 or 2, wherein the sheet comprises glass. The method of claim 1 or 2, wherein the thickness of the sheet 300 microns. The method of claim 1 or 2, wherein the surface modifying layer has a thickness of from 0.1 nm to 100 nm. The method of claim 1 or 2, wherein the surface modifying layer comprises a) a plasma polymerized fluoropolymer; and b) an aromatic decane.